WO2019188747A1 - Gallium compound semiconductor substrate polishing composition - Google Patents
Gallium compound semiconductor substrate polishing composition Download PDFInfo
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- WO2019188747A1 WO2019188747A1 PCT/JP2019/011978 JP2019011978W WO2019188747A1 WO 2019188747 A1 WO2019188747 A1 WO 2019188747A1 JP 2019011978 W JP2019011978 W JP 2019011978W WO 2019188747 A1 WO2019188747 A1 WO 2019188747A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polishing
- compound
- slurry
- acid
- less
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 759
- 239000000203 mixture Substances 0.000 title claims abstract description 282
- 239000000758 substrate Substances 0.000 title claims abstract description 65
- 239000004065 semiconductor Substances 0.000 title claims abstract description 47
- 150000002259 gallium compounds Chemical class 0.000 title claims abstract description 39
- 239000002002 slurry Substances 0.000 claims abstract description 173
- 239000006061 abrasive grain Substances 0.000 claims abstract description 165
- 150000001875 compounds Chemical class 0.000 claims abstract description 119
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 113
- 238000000034 method Methods 0.000 claims abstract description 94
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 50
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims description 120
- 239000007800 oxidant agent Substances 0.000 claims description 89
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 69
- 239000007788 liquid Substances 0.000 claims description 58
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 31
- 229910002601 GaN Inorganic materials 0.000 claims description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 21
- 229920002635 polyurethane Polymers 0.000 claims description 16
- 239000004814 polyurethane Substances 0.000 claims description 16
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 16
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 15
- 125000005907 alkyl ester group Chemical group 0.000 claims description 11
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 10
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 9
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 7
- 239000013522 chelant Substances 0.000 claims description 6
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 39
- 239000000463 material Substances 0.000 description 27
- 238000007517 polishing process Methods 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 21
- 230000003746 surface roughness Effects 0.000 description 18
- 239000011163 secondary particle Substances 0.000 description 17
- 239000002245 particle Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 15
- 235000012431 wafers Nutrition 0.000 description 15
- 230000001590 oxidative effect Effects 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 13
- 150000007513 acids Chemical class 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 229910044991 metal oxide Inorganic materials 0.000 description 12
- 150000004706 metal oxides Chemical class 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- -1 silane compound Chemical class 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000000227 grinding Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 238000000089 atomic force micrograph Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000008119 colloidal silica Substances 0.000 description 7
- 239000006260 foam Substances 0.000 description 7
- 230000001771 impaired effect Effects 0.000 description 7
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical class O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000010432 diamond Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 6
- 230000001629 suppression Effects 0.000 description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 description 6
- 229920005830 Polyurethane Foam Polymers 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 description 5
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 5
- 150000004767 nitrides Chemical class 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- 239000011496 polyurethane foam Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Chemical class O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- 229910000423 chromium oxide Inorganic materials 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 229910003460 diamond Inorganic materials 0.000 description 4
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 4
- 150000005690 diesters Chemical class 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 150000002823 nitrates Chemical class 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical class OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical class O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910052580 B4C Inorganic materials 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 3
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- ICIWUVCWSCSTAQ-UHFFFAOYSA-N iodic acid Chemical class OI(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-N 0.000 description 3
- 150000004715 keto acids Chemical class 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000003223 protective agent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- QQVDJLLNRSOCEL-UHFFFAOYSA-N (2-aminoethyl)phosphonic acid Chemical compound [NH3+]CCP(O)([O-])=O QQVDJLLNRSOCEL-UHFFFAOYSA-N 0.000 description 2
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 2
- RAEOEMDZDMCHJA-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-[2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]ethyl]amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CCN(CC(O)=O)CC(O)=O)CC(O)=O RAEOEMDZDMCHJA-UHFFFAOYSA-N 0.000 description 2
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 description 2
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 description 2
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 239000004153 Potassium bromate Substances 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 230000000843 anti-fungal effect Effects 0.000 description 2
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- 229940121375 antifungal agent Drugs 0.000 description 2
- ZRDJERPXCFOFCP-UHFFFAOYSA-N azane;iodic acid Chemical compound [NH4+].[O-]I(=O)=O ZRDJERPXCFOFCP-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical class OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical class OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
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- 239000000470 constituent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
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- DRHRVHMGRBEOTK-UHFFFAOYSA-N hydrogen peroxide;nitrate Chemical class OO.[O-][N+]([O-])=O DRHRVHMGRBEOTK-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910000462 iron(III) oxide hydroxide Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 229940094037 potassium bromate Drugs 0.000 description 2
- 235000019396 potassium bromate Nutrition 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- IFIDXBCRSWOUSB-UHFFFAOYSA-N potassium;1,3-dichloro-1,3,5-triazinane-2,4,6-trione Chemical compound [K+].ClN1C(=O)NC(=O)N(Cl)C1=O IFIDXBCRSWOUSB-UHFFFAOYSA-N 0.000 description 2
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- SFRLSTJPMFGBDP-UHFFFAOYSA-N 1,2-diphosphonoethylphosphonic acid Chemical compound OP(O)(=O)CC(P(O)(O)=O)P(O)(O)=O SFRLSTJPMFGBDP-UHFFFAOYSA-N 0.000 description 1
- MXYOPVWZZKEAGX-UHFFFAOYSA-N 1-phosphonoethylphosphonic acid Chemical compound OP(=O)(O)C(C)P(O)(O)=O MXYOPVWZZKEAGX-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- INJFRROOFQOUGJ-UHFFFAOYSA-N 2-[hydroxy(methoxy)phosphoryl]butanedioic acid Chemical compound COP(O)(=O)C(C(O)=O)CC(O)=O INJFRROOFQOUGJ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical class CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 229910002704 AlGaN Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- WNTGHAZFHMDMCZ-UHFFFAOYSA-N ClC12NC(NC1(NC(N(C2=O)[N+]#[C-])=O)Cl)=O Chemical compound ClC12NC(NC1(NC(N(C2=O)[N+]#[C-])=O)Cl)=O WNTGHAZFHMDMCZ-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- RUSUZAGBORAKPY-UHFFFAOYSA-N acetic acid;n'-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine Chemical group CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCNCCN RUSUZAGBORAKPY-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052795 boron group element Inorganic materials 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Chemical class [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000008504 concentrate Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-L ethyl phosphate(2-) Chemical compound CCOP([O-])([O-])=O ZJXZSIYSNXKHEA-UHFFFAOYSA-L 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- GTTBQSNGUYHPNK-UHFFFAOYSA-N hydroxymethylphosphonic acid Chemical compound OCP(O)(O)=O GTTBQSNGUYHPNK-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- CVMIVKAWUQZOBP-UHFFFAOYSA-L manganic acid Chemical class O[Mn](O)(=O)=O CVMIVKAWUQZOBP-UHFFFAOYSA-L 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/02008—Multistep processes
- H01L21/0201—Specific process step
- H01L21/02024—Mirror polishing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
Definitions
- the present invention relates to a polishing composition, and more particularly to a polishing composition used for polishing a gallium compound semiconductor substrate.
- the present invention also relates to a method for polishing a gallium compound semiconductor substrate and a polishing composition set used in the method.
- Patent Documents 1 to 3 are listed as technical documents related to polishing of a nitride semiconductor substrate such as gallium nitride.
- Compound semiconductors are generally very chemically stable and have low reactivity, and some of them have extremely high hardness such as gallium nitride, and processing by polishing is generally not easy. For this reason, a compound semiconductor substrate is usually subjected to polishing (wrapping) performed by supplying diamond abrasive grains to a polishing surface plate, and then a polishing pad and an object to be polished are removed in order to remove scratches caused by the lapping or the like. Polishing (polishing) performed by supplying a slurry containing abrasive grains between them and chemical etching using a solution containing no abrasive grains is performed.
- Patent Documents 1 and 2 relate to a technique for polishing a nitride semiconductor crystal using a slurry containing abrasive grains, and aim to improve the polishing rate mainly by examining the particle diameter of the abrasive grains.
- the surface quality required for the compound semiconductor substrate tends to gradually increase, and the techniques described in Patent Documents 1 and 2 cannot sufficiently cope with the surface quality.
- Patent Document 3 proposes that a gallium nitride semiconductor substrate polished (primary polishing) using the first polishing composition is further polished (secondary polishing) using the second polishing composition. ing.
- secondary polishing second polishing.
- the technique described in Patent Document 3 has not been able to sufficiently respond.
- the present invention has been made in view of the above circumstances, and its purpose is used for polishing gallium nitride and other gallium compound semiconductor substrates, and has a high polishing efficiency and a higher quality surface after polishing. It is providing the polishing composition which can be compatible. Another related object is to provide a method of polishing a gallium compound semiconductor substrate using the polishing composition. Still another object is to provide a polishing method that can efficiently realize a high-quality surface of a gallium nitride or other gallium compound semiconductor substrate. Another related object is to provide a polishing composition set suitable for realizing such a polishing method.
- a polishing composition used for polishing a gallium compound semiconductor substrate includes silica abrasive grains, a compound C pho having a phosphoric acid group or a phosphonic acid group (hereinafter sometimes simply referred to as “compound C pho ”), and water.
- the polishing composition does not contain an oxidizing agent.
- silica abrasive grains such a polishing composition can more efficiently remove the surface of a gallium compound semiconductor substrate that is an object to be polished than etching using a solution that does not contain abrasive grains.
- the compound Cpho and not containing an oxidizing agent it is possible to suppress the surface of the polishing object from being roughened by polishing and to improve the surface quality after polishing.
- examples of the compound C pho include (A) a chelate compound having a phosphonic acid group, (B) a mono-C 1-4 alkyl ester of phosphoric acid, and di-C 1-4 phosphate.
- the polishing composition disclosed herein preferably has a pH of less than 2. According to the polishing composition having a pH of less than 2, a surface having high surface quality can be efficiently realized.
- the polishing composition disclosed herein may further contain an acid.
- an acid By using the compound Cpho and an acid in combination, good surface quality can be efficiently realized.
- the compound mpho content m1 [mol / kg] and the acid content m2 [mol / kg] in the polishing composition should be set so as to satisfy the following formula: m1 / (m1 + m2) ⁇ 0.1; Is preferred.
- the polishing composition disclosed herein is suitable as a polishing composition for polishing a gallium nitride substrate or a gallium oxide substrate.
- a method for polishing a gallium compound semiconductor substrate includes supplying any of the polishing compositions disclosed herein to a gallium compound semiconductor substrate and polishing the substrate. According to this polishing method, the surface quality of the gallium compound semiconductor substrate can be effectively improved.
- a method for polishing a gallium compound semiconductor substrate (hereinafter sometimes referred to as “polishing object”) is provided.
- the polishing method includes, in this order, a first polishing step for polishing with a slurry S1 containing abrasive grains A1 and water, and a second polishing step for polishing with a slurry S2 containing abrasive grains A2 and water.
- the abrasive grain A2 includes silica abrasive grains.
- the slurry S2 further includes a compound Cpho having a phosphoric acid group or a phosphonic acid group.
- the slurry S1 is does not contain the above-mentioned compound C pho, or the concentration of the compound C pho [wt%] is lower than the concentration [wt%] of the above compound C pho in the slurry S2. According to this polishing method, the polishing object polished using the slurry S1 is further polished using the slurry S2 containing the compound Cpho , thereby suppressing increase in polishing time and high-quality surface after polishing. It can be compatible.
- the pH of the slurry S1 can be less than 2.0. According to such a low pH slurry S1, high polishing efficiency is easily obtained in the first polishing step.
- a slurry S1 containing a strong acid can be preferably employed.
- a strong acid By using a strong acid, the pH of the slurry S1 can be controlled efficiently.
- the slurry S1 may include an oxidizing agent.
- an oxidizing agent at least one selected from the group consisting of permanganate, metavanadate and persulfate can be preferably used.
- the abrasive grains A1 can include silica abrasive grains.
- the pH of the slurry S2 can be less than 3.0. According to the low pH slurry S2, high polishing efficiency is easily obtained in the second polishing step. Further, when the slurry S2 contains the compound Cpho , the surface of the object to be polished can be prevented from being rough even at a low pH, and a high-quality surface can be obtained after polishing.
- the concentration of the compound Cpho in the slurry S2 can be, for example, 0.2 wt% or more and 15 wt% or less.
- concentration of the compound C pho is in the above range, in the second polishing step, both high polishing efficiency and high-quality surface after polishing can be suitably achieved.
- the polishing pad used for polishing in the second polishing step is preferably a polishing pad having a surface made of soft polyurethane foam.
- the polishing composition set includes the slurry S1 or a composition Q1 which is a concentrated liquid thereof, and the slurry S2 or a composition Q2 which is a concentrated liquid thereof.
- the composition Q1 and the composition Q2 are stored separately from each other. It can implement suitably using the polishing composition set of such a structure.
- the matter disclosed by this specification includes a polishing composition used in the second polishing step in any of the polishing methods disclosed herein, the polishing composition being the slurry S2 or a concentrated liquid thereof.
- the polishing composition can be preferably used as the composition Q2 constituting the polishing composition set disclosed herein.
- the pH of the slurry S2 can be, for example, less than 3.0, less than 2.0, or less than 1.5.
- the technique disclosed here is applied to polishing using a gallium compound semiconductor substrate as an object to be polished.
- the concept of the gallium compound semiconductor in this specification includes, in addition to gallium nitride (GaN) and gallium oxide (Ga 2 O 3 ), a part of Ga in these is another group 13 element of the periodic table (B, Al, In ), For example, AlGaN, GaInN, AlGaInN, and the like.
- the technique disclosed herein can be preferably applied to polishing of a substrate having a surface made of such a gallium compound semiconductor material.
- the surface that is, the surface to be polished may be a surface made of any one type of gallium compound semiconductor material, for example, a surface of a single crystal of the material, or a surface made of a mixture of two or more types of gallium compound semiconductor materials.
- the gallium compound semiconductor substrate may be a self-supporting gallium compound semiconductor wafer, or may have a gallium compound semiconductor crystal on an appropriate underlayer. Examples of such an underlayer include a sapphire substrate, a silicon substrate, a SiC substrate, and the like.
- the gallium compound semiconductor may be doped for the purpose of imparting conductivity or the like, or may be non-doped.
- Examples of a preferable application target of the technology disclosed herein include a gallium nitride substrate and a gallium oxide substrate.
- the gallium oxide substrate typically has a surface made of ⁇ -Ga 2 O 3 crystals, and preferably has a surface made of ⁇ -Ga 2 O 3 single crystals.
- the gallium nitride substrate typically has a surface made of GaN crystals, and preferably has a surface made of GaN single crystals.
- the surface index of the main surface of the GaN crystal, that is, the surface to be polished is not particularly limited. Examples of the surface to be polished include a polar surface such as a C surface; a nonpolar surface such as an A surface and an M surface; a semipolar surface;
- the polishing composition disclosed herein contains abrasive grains. According to polishing using a polishing composition containing abrasive grains, for example, scratches generated on a polishing object in a previous process such as lapping can be more efficiently compared to chemical etching using a solution that does not contain solid particles such as abrasive grains. Can be removed. In addition, according to the polishing composition disclosed herein, the scratches can be efficiently removed while suppressing surface roughness due to polishing by including the compound Cpho described later.
- the polishing composition disclosed herein contains at least silica abrasive grains as the abrasive grains. According to the polishing composition containing silica abrasive grains, high surface quality is easily obtained.
- the silica abrasive grains can be used by appropriately selecting from various known silica particles. Examples of such known silica particles include colloidal silica and dry silica. Of these, the use of colloidal silica is preferred. According to the silica abrasive grains containing colloidal silica, a high polishing rate and good surface accuracy can be suitably achieved.
- colloidal silica examples include silica produced using an alkali silicate-containing liquid (for example, sodium silicate-containing liquid) containing an alkali metal such as Na or K and SiO 2 as a raw material, tetraethoxy Silica (alkoxide method silica) produced by hydrolysis condensation reaction of alkoxysilane such as silane or tetramethoxysilane is included.
- alkali silicate-containing liquid for example, sodium silicate-containing liquid
- alkali metal such as Na or K and SiO 2
- tetraethoxy Silica alkoxide method silica
- dry silica examples include silica obtained by burning a silane compound such as silicon tetrachloride or trichlorosilane in a hydrogen flame (fumed silica), or by reaction between metallic silicon and oxygen. The resulting silica is included.
- the polishing composition disclosed herein contains abrasive grains made of a material other than silica (hereinafter also referred to as non-silica abrasive grains) in addition to silica abrasive grains, as long as the effects of the present invention are not impaired. May be.
- abrasive grains made of a material other than silica hereinafter also referred to as non-silica abrasive grains
- constituent materials of such non-silica abrasive grains include oxides such as aluminum oxide, cerium oxide, chromium oxide, titanium dioxide, zirconium oxide, magnesium oxide, manganese oxide, zinc oxide, iron oxide particles; silicon nitride, nitriding Examples thereof include nitrides such as boron; carbides such as silicon carbide and boron carbide particles; diamond;
- Surface-modified abrasive grains may be used. Specifically, the surface modification of the abrasive grain is performed by attaching or bonding a substance having a potential different from that of the abrasive grain surface to the abrasive grain surface and changing the potential of the abrasive grain surface.
- the material used to change the potential of the abrasive grain surface are silicon oxide, surfactants, inorganic acids, organic acids, aluminum oxide, etc. Metal oxides can be used.
- the technique disclosed herein can be preferably implemented in a mode in which the proportion of silica abrasive grains is greater than 70 wt% of the total weight of abrasive grains contained in the polishing composition from the viewpoint of improving the surface quality after polishing. .
- the ratio of the silica abrasive grains is more preferably 90% by weight or more, further preferably 95% by weight or more, and particularly preferably 99% by weight or more.
- a polishing composition in which 100% by weight of the abrasive grains contained in the polishing composition is silica abrasive grains is preferable.
- the average secondary particle diameter of the abrasive grains contained in the polishing composition is suitably 5 nm or more, preferably 10 nm or more, more preferably 20 nm or more. As the average secondary particle diameter of the abrasive grains increases, the polishing efficiency of the object to be polished by the polishing composition tends to improve. In some embodiments, the average secondary particle size of the abrasive grains may be 35 nm or more, and may be 50 nm or more.
- the average secondary particle diameter of the abrasive is suitably 300 nm or less, preferably 200 nm or less, more preferably 150 nm or less, and may be 100 nm or less or 80 nm or less.
- the average secondary particle diameter of the abrasive grains refers to a volume average particle diameter (volume average diameter D50) based on a dynamic light scattering method.
- the average secondary particle size of the abrasive grains can be measured using a commercially available dynamic light scattering particle size analyzer, for example, using a model “UPA-UT151” manufactured by Nikkiso Co., Ltd. or an equivalent thereof. be able to.
- the abrasive grains contained in the polishing composition may be one type, or two or more types having different materials, particle shapes, or particle sizes. From the viewpoint of the dispersion stability of the abrasive grains and the quality stability of the polishing composition, the polishing composition according to some embodiments is 90% by weight or more, more preferably 95% of the abrasive grains contained in the composition. % By weight or more, more preferably 99% by weight or more may be one type of silica abrasive.
- the polishing composition disclosed herein can be preferably implemented, for example, in an embodiment containing only one type of silica abrasive as the abrasive.
- the concentration of abrasive grains in the polishing composition is not particularly limited.
- the concentration of the abrasive grains may be, for example, 5% by weight or more, 12% by weight or more, 17% by weight or more, or 22% by weight or more.
- the concentration of the abrasive grains is usually appropriately 50% by weight or less, and 40% by weight or less. Is preferred.
- the polishing composition disclosed herein can also be preferably implemented in an embodiment in which the abrasive concentration is 35% by weight or less or 30% by weight or less.
- the polishing composition disclosed herein contains water as an essential component.
- water ion exchange water (deionized water), pure water, ultrapure water, distilled water and the like can be preferably used.
- the polishing composition disclosed herein may further contain an organic solvent (lower alcohol, lower ketone, etc.) that can be uniformly mixed with water, if necessary.
- 90% by volume or more of the solvent contained in the polishing composition is preferably water, and more preferably 95% by volume or more (typically 99 to 100% by volume) is water.
- the polishing composition disclosed here contains a compound Cpho having a phosphate group or a phosphonic acid group as an essential component.
- a polishing composition containing abrasive grains By including the compound Cpho in a polishing composition containing abrasive grains, it is possible to suppress the surface roughness of the polishing object due to polishing and improve the surface quality after polishing. Thereby, the surface where surface roughness Ra is small and generation
- Compound Cpho can be used alone or in combination of two or more.
- the compound Cpho may be an inorganic compound or an organic compound.
- Examples of the compound Cpho which is an inorganic compound, include phosphoric acid (H 2 PO 4 ), phosphorous acid (H 3 PO 3 ), and inorganic salts thereof.
- the inorganic salt can be, for example, an alkali metal salt such as a sodium salt, a potassium salt, or a lithium salt.
- Specific examples of inorganic salts of phosphoric acid include alkali metal phosphoric acid such as tripotassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, trisodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, etc. Salts and alkali metal hydrogen phosphates.
- compound Cpho contained in polishing composition may contain the tautomer.
- a polishing composition containing phosphorous acid as compound Cpho may contain phosphonic acid, which is a tautomer thereof, together with phosphorous acid.
- Examples of the compound Cpho which is an organic compound, include phosphate esters and phosphites.
- phosphate esters monoesters and diesters are preferably used, and a mixture of monoesters and diesters may be used.
- the molar ratio of monoester to diester in the above mixture may be, for example, 20:80 to 80:20, or 40:60 to 60:40.
- a monoester can be used preferably.
- the organic group that forms an ester bond with phosphoric acid or phosphorous acid is preferably a hydrocarbon group of about C 1-20 , more preferably a C 1-12 hydrocarbon group, and a C 1-8 hydrocarbon group. More preferred is a C 1-4 hydrocarbon group.
- C XY means “the number of carbon atoms is X or more and Y or less”.
- the hydrocarbon group may be aliphatic or aromatic.
- the aliphatic hydrocarbon group may be saturated or unsaturated, may be linear or cyclic, and may be linear or branched.
- the compound C pho includes at least one selected from the group consisting of mono-C 1-4 alkyl esters of phosphoric acid and di-C 1-4 alkyl esters of phosphoric acid. It can be preferably used.
- a mixture of monoethyl phosphate and diethyl phosphate can be used as the compound Cpho .
- the compound Cpho which is an organic compound, may be a chelate compound having a phosphonic acid group.
- Examples of such compounds C pho 1-hydroxyethylidene-1,1-diphosphonic acid, amino tri (methylene phosphonic acid), ethylenediamine tetra (methylene phosphonic acid), diethylenetriamine penta (methylene phosphonic acid), ethane-1, 1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane-1,2- Chelate compounds having two or more phosphonic acid groups in one molecule, such as dicarboxy-1,2-diphosphonic acid; 2-aminoethylphosphonic acid, methanehydroxyphosphonic acid, 2-phosphonobutane-1,2-dicarboxylic acid 1-phosphonobutane-2,3,4-tricarboxylic acid, ⁇ -methylphospho
- Chelate compounds with one phosphonic acid group in, and the like are advantageously 1 or more and 4 or less per molecule. It is preferably 1 or more and 3 or less, particularly preferably 1 or 2. From the same viewpoint, the molecular weight of the compound Cpho is advantageously 800 or less, preferably 600 or less, more preferably 400 or less, and further preferably 300 or less or 250 or less.
- Other examples of the compound Cpho which is an organic compound, include a salt of phosphoric acid or phosphorous acid and an organic cation.
- the polishing composition disclosed herein includes, as compound Cpho , (A) a chelate compound having a phosphonic acid group, (B) phosphoric acid mono-C 1-4 alkyl ester, phosphoric acid di-C 1-4 alkyl ester, and A compound selected from the group consisting of mono-C 1-4 alkyl esters of phosphorous acid, (C) at least one of phosphoric acid and phosphorous acid, (D) a group consisting of inorganic salt of phosphoric acid and inorganic salt of phosphorous acid It can implement preferably in the aspect using at least any one of the compounds selected from these.
- the compound C pho may contain two or more compounds selected from any one of the above (A) to (D), and is selected from two or more of the above (A) to (D) Two or more compounds may be included.
- the compound C pho may contain only one kind of compound selected from any one of the above (A) to (D).
- the concentration [wt%] of Compound Cpho in the polishing composition is not particularly limited. This concentration is usually suitably 0.05% by weight or more, preferably 0.08% by weight or more, more preferably 0.15% by weight or more, and 0.2% by weight. It may be more than 0.4% by weight. Surface quality after polishing generally tends to improve with increasing concentration of compound Cpho . In some embodiments, the concentration of Compound Cpho may be 0.5 wt% or more, greater than 0.5 wt%, 0.8 wt% or more, 2.5 wt% or more, 4 It may be 0.0% by weight or more.
- the concentration of the compound C pho is usually suitably 25% by weight or less, preferably 20% by weight or less, preferably 15% by weight or less. But you can. In some embodiments, the concentration of compound C pho may be, for example, 10 wt% or less, 6 wt% or less, 3 wt% or less, 1.5 wt% or less, 1.0 wt% % Or less may be sufficient.
- the concentration of the compound C pho described above is the concentration of the compound C pho in the polishing composition when supplied to the object to be polished for use in polishing, that is, when the composition is used (Point-of-Use; POU).
- concentration of compound Cpho in the polishing composition when supplied to the object to be polished is also referred to as “working slurry”.
- polishing compositions disclosed herein abrasive content (abrasive concentration) of the compound C pho at 25 wt% concentration, it is preferable to satisfy the concentration of the compound C pho described above.
- concentration of compound C pho in abrasive concentration of 25 wt% abrasive concentration refers to the concentration of converted compounds C pho so that 25 wt%.
- abrasive concentration is X wt%
- concentration of the compound C pho is Y wt%
- the following formula: Y ⁇ (25 / X) ; a calculate the concentration of the compound C pho in abrasive concentration of 25 wt% can do.
- the polishing composition disclosed herein may contain an oxidizer as necessary, as long as the effects of the present invention are not significantly impaired.
- the concentration of the oxidizing agent can be, for example, more than 0% by weight and 5.0% by weight or less.
- the polishing composition preferably has an oxidant concentration of a predetermined level or less, and may not contain an oxidant.
- the concentration of the oxidizing agent is preferably not more than a predetermined value.
- an oxidizing agent such as hydrogen peroxide (H 2 O 2 ) is included for the purpose of promoting polishing.
- H 2 O 2 hydrogen peroxide
- the polishing composition containing silica abrasive grains and Compound Cpho impairs the surface quality improvement effect of Compound Cpho by containing an oxidizing agent. Therefore, in some embodiments of the polishing composition disclosed by this specification, it is preferable that the polishing composition has a concentration of an oxidizing agent or less.
- the concentration of the oxidizing agent in the polishing composition is preferably less than 0.1% by weight, more preferably less than 0.05% by weight, still more preferably less than 0.02% by weight, particularly preferably 0.01% by weight. %. In one embodiment of the polishing composition disclosed in the present specification, it is desirable that the polishing composition does not contain an oxidizing agent.
- the polishing composition disclosed herein can be preferably implemented in an embodiment that does not contain at least hydrogen peroxide, sodium persulfate, potassium persulfate, ammonium persulfate, or sodium dichloroisocyanurate.
- the polishing composition does not contain an oxidizing agent means that at least intentionally no oxidizing agent is blended, and that a trace amount of an oxidizing agent is inevitably contained due to raw materials and manufacturing methods. May be acceptable.
- the trace amount means that the molar concentration of the oxidizing agent in the polishing composition is 0.0005 mol / L or less (preferably 0.0001 mol / L or less, more preferably 0.00001 mol / L or less, particularly preferably 0.00. 00000 mol / L or less). It is preferable that the concentration of the oxidizing agent is zero or below the detection limit.
- the polishing composition disclosed herein preferably has a pH of less than 5.0, preferably less than 3.0. By using a polishing composition having a lower pH, the polishing efficiency tends to be improved. In some embodiments, the polishing composition may have a pH of, for example, 2.5 or less, less than 2.5, less than 2.0, less than 1.5, or less than 1.3. Good. According to the polishing composition disclosed here, when the composition contains the compound Cpho , it is possible to effectively suppress the roughness of the surface of the polishing object even at a low pH. This makes it possible to achieve both good polishing efficiency and high surface quality.
- the lower limit of the pH of the polishing composition is not particularly limited, but it is usually suitably 0.5 or more and 0.7 or more from the viewpoint of inhibiting corrosion of equipment and environmental hygiene.
- pH is measured using a pH meter, standard buffer solution (phthalate pH buffer solution pH: 4.01 (25 ° C.), neutral phosphate pH buffer solution pH: 6.86 ( 25 ° C.), after calibrating three points using a carbonate pH buffer solution (pH: 10.01 (25 ° C.)), the glass electrode was put into the composition to be measured, and after 2 minutes had elapsed, the glass electrode was stabilized. Can be determined by measuring the value of.
- a glass electrode type hydrogen ion concentration indicator (model number F-23) manufactured by HORIBA, Ltd. or an equivalent thereof is used.
- the polishing composition disclosed herein includes one or two or more acids as optional components used for the purpose of adjusting pH, etc., if necessary, in addition to the essential components of abrasive grains, water and compound Cpho. May be included. Acids corresponding to the compound Cpho , that is, phosphoric acid, phosphorous acid, and phosphonic acid are not included in the examples of acids mentioned here.
- acids include inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphinic acid, boric acid; acetic acid, itaconic acid, succinic acid, tartaric acid, citric acid, maleic acid, glycolic acid, malonic acid, methanesulfonic acid, formic acid And organic acids such as malic acid, gluconic acid, alanine, glycine, lactic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and the like.
- the acid may be used in the form of a salt of the acid.
- the acid salt may be, for example, an alkali metal salt such as a sodium salt or a potassium salt, or an ammonium salt.
- the polishing composition according to some embodiments includes a combination of compound Cpho and a strong acid.
- the strong acid preferably has a pKa of less than 1, more preferably a pKa of less than 0.5, and even more preferably a pKa of less than 0.
- oxo acid is preferable.
- strong acids that can be used in the polishing composition disclosed herein include hydrochloric acid, sulfuric acid, and nitric acid.
- the concentration of the acid is not particularly limited, and can be set as appropriate so that the effects of the present invention are not significantly impaired.
- the acid concentration may be, for example, 0.05% by weight or more, 0.1% by weight or more, or 0.3% by weight or more.
- the acid concentration may be, for example, less than 5 wt%, less than 3 wt%, less than 1.5 wt%, It may be less than 1% by weight or less than 1.0% by weight.
- the acid concentration described above can be preferably applied to the concentration of strong acid (especially oxo acid) among acids.
- the acid concentration at an abrasive concentration of 25% by weight preferably satisfies the acid concentration described above.
- the acid concentration at an abrasive concentration of 25% by weight can be calculated in the same manner as the concentration of compound Cpho at an abrasive concentration of 25% by weight.
- the total of the concentration w1 [wt%] of the compound Cpho and the concentration w2 [wt%] of the acid (preferably strong acid) in the polishing composition is, for example, 0.1 wt% or more From the viewpoint of achieving a higher level of polishing efficiency and surface quality after polishing, it is usually preferably 0.3% by weight or more, and may be 0.5% by weight or more, or 0.7% by weight or more. But you can.
- the w1 + w2 may be, for example, 30% by weight or less, and is usually preferably 25% by weight or less, preferably 20% by weight or less, and 15% by weight or less, from the viewpoint of achieving a higher level of polishing efficiency and surface quality after polishing. It may be less than or equal to 10% by weight.
- the polishing composition disclosed herein is also preferably implemented in an embodiment in which the above w1 + w2 is, for example, 5% by weight or less, 3% by weight or less, 2% by weight or less, 1.5% by weight or less, or 1.4% by weight or less. Can be done.
- the polishing composition disclosed herein contains the compound C pho and an acid (preferably a strong acid) in combination, their contents are the compound m pho content m1 [mol / kg] and the acid content.
- the relationship with m2 [mol / kg] is as follows: m1 / (m1 + m2) ⁇ 0.1; Can be set to satisfy. That is, on a molar basis, is preferably 10% or more of the total amount of the compound C pho and acid contained per polishing composition 1kg is a compound C pho.
- m1 / (m1 + m2) is 0.15 or more or 0.20 or more, a more preferable result can be realized.
- m1 / (m1 + m2) is typically less than 1 and may be less than 0.95 or less than 0.90.
- polishing compositions disclosed herein are compounds C pho and acid (preferably a strong acid) belonging to the (C) in combination and the content of compound C pho above (C) M1c [mol / kg]
- m1C / (m1C + m2) is 0.30 or more, for example.
- m1C / (m1C + m2) is preferably 0.40 or more, more preferably 0.55 or more, and may be 0.70 or more.
- m1C / (m1C + m2) is typically less than 1, and may be less than 0.95 or less than 0.90 from the viewpoint of improving the polishing efficiency.
- the polishing composition disclosed herein contains a combination of the compound C pho belonging to the above (A) and an acid (preferably a strong acid), the content m1A [mol / kg] of the compound C pho of the above (A) Can be set so that m1A / (m1A + m2) is 0.15 or more, for example. From the viewpoint of improving the surface quality after polishing, m1A / (m1A + m2) is preferably 0.20 or more. m1A / (m1A + m2) is typically less than 1, and may be less than 0.90 or less than 0.80, less than 0.70, or less than 0.60 from the viewpoint of improving polishing efficiency.
- m1A / (m1A + m2) may be less than 0.50, less than 0.40, and less than 0.30.
- the compound C pho and acid polishing compositions disclosed herein belongs to the (B) (preferably In the case of containing a combination of (strong acid) and the compound C pho content m1B of the above (B) and the acid content m2, the polishing composition disclosed here is a compound C belonging to the above (D) pho and the acid (preferably a strong acid) may be preferably applied to a relationship between the content m2 content m1D and acid compound C pho (D) above in a case that includes a combination of a.
- the polishing composition disclosed herein is a chelating agent, a thickening agent, a dispersant, a surface protecting agent, a wetting agent, an organic or inorganic base, a surfactant, and a rust-proofing agent as long as the effects of the present invention are not impaired.
- Known additives that can be used in polishing compositions typically high-hardness material polishing compositions such as gallium nitride substrate polishing compositions), such as agents, preservatives, and fungicides, as needed. It may be further contained.
- each component contained in the polishing composition may be mixed using a well-known mixing device such as a blade-type stirrer, an ultrasonic disperser, or a homomixer.
- a well-known mixing device such as a blade-type stirrer, an ultrasonic disperser, or a homomixer.
- the aspect which mixes these components is not specifically limited, For example, all the components may be mixed at once and may be mixed in the order set suitably.
- the polishing composition disclosed herein may be a one-part type or a multi-part type including a two-part type.
- the liquid A containing a part of the constituent components (typically components other than the solvent) of the polishing composition and the liquid B containing the remaining components are mixed to polish the polishing object. It may be configured to be used.
- the polishing composition disclosed herein may be in a concentrated form (that is, in the form of a concentrated concentrate of polishing liquid) before being supplied to the object to be polished.
- the polishing composition in such a concentrated form is advantageous from the viewpoints of convenience, cost reduction, etc. during production, distribution, storage and the like.
- the concentration rate can be, for example, about 1.2 to 5 times in terms of volume.
- the polishing composition in the form of a concentrated liquid can be used in such a manner that a polishing liquid is prepared by diluting at a desired timing and the polishing liquid is supplied to an object to be polished.
- the dilution can be typically performed by adding the aforementioned solvent to the concentrated solution and mixing.
- the said solvent is a mixed solvent
- some of these agents may be diluted and then mixed with other agents to prepare a polishing liquid. After mixing a plurality of agents, the mixture is diluted.
- a polishing liquid may be prepared.
- the polishing composition disclosed herein can be used for polishing a polishing object, for example, in an embodiment including the following operations. That is, a polishing liquid containing any of the polishing compositions disclosed herein is prepared. Preparing the polishing liquid can include diluting the polishing composition. Or you may use the said polishing composition as polishing liquid as it is. Further, in the case of a multi-drug type polishing composition, to prepare the polishing liquid, mixing those agents, diluting one or more agents before the mixing, and after the mixing Diluting the mixture, etc. can be included. Next, the polishing liquid is supplied to the surface of the object to be polished and polished by a conventional method.
- a polishing object is set in a general polishing apparatus, and the polishing liquid is supplied to the surface (polishing object surface) of the polishing object through a polishing pad of the polishing apparatus.
- the polishing pad is pressed against the surface of the object to be polished, and both are relatively moved (for example, rotated). The polishing of the object to be polished is completed through the polishing step.
- a polishing method for polishing a material to be polished and a method for manufacturing a polished article using the polishing method are provided.
- the above polishing method is characterized by including a step of polishing an object to be polished using the polishing composition disclosed herein.
- a polishing method according to a preferred embodiment includes a step of performing preliminary polishing (preliminary polishing step) and a step of performing final polishing (final polishing step).
- the preliminary polishing step is a step of performing preliminary polishing on an object to be polished.
- the preliminary polishing step is a polishing step that is arranged immediately before the finish polishing step.
- the final polishing step here is a step of performing final polishing on the polishing object that has been subjected to preliminary polishing, and is the last of the polishing steps performed using the polishing composition containing abrasive grains. It refers to a polishing step that is arranged (ie, on the most downstream side).
- the polishing composition disclosed herein may be used in the preliminary polishing step, may be used in the final polishing step, or preliminarily polished. It may be used in both the process and the finish polishing process.
- the polishing step using the polishing composition is a finish polishing step.
- the polishing composition disclosed herein can realize a high-quality surface with small surface roughness Ra after polishing and suppressed generation of pits, and is therefore used in the final polishing step of the surface of the material to be polished. It can be particularly preferably used as a polishing composition (finish polishing composition).
- the preliminary polishing step performed prior to the final polishing step typically includes a preliminary polishing step composition containing abrasive grains and water. Is done using.
- the abrasive grains contained in the preliminary polishing step composition may be referred to as preliminary polishing abrasive grains.
- the material and properties of the pre-polishing abrasive grains are not particularly limited.
- materials that can be used as the pre-polishing abrasive include silica particles, alumina, cerium oxide, chromium oxide, titanium dioxide, zirconium oxide, magnesium oxide, manganese dioxide, zinc oxide, iron oxide, and the like; silicon nitride Abrasive grains substantially composed of any one of: nitrides such as boron nitride; carbides such as silicon carbide and boron carbide; diamonds; carbonates such as calcium carbonate and barium carbonate; Silica abrasive and alumina abrasive are particularly preferred.
- ⁇ -alumina is typically used as the alumina abrasive grains.
- composition of the abrasive grains “substantially consisting of X” or “substantially consisting of X” means that the proportion of X in the abrasive grains (the purity of X) is weight. It is 90% or more on the basis (preferably 95% or more, more preferably 97% or more, further preferably 98% or more, for example 99% or more).
- the average secondary particle size of the pre-polishing abrasive grains is usually 20 nm or more, and preferably 35 nm or more, more preferably 50 nm or more, and 60 nm or more from the viewpoint of polishing efficiency. Further, from the viewpoint of facilitating improving the surface quality in the final polishing step, the average secondary particle diameter of the preliminary polishing abrasive grains is usually appropriately 2000 nm or less, and may be 1000 nm or less, 800 nm or less, or 600 nm or less, or 300 nm or less. 200 nm or less, 150 nm or less, 100 nm or less, or 80 nm or less. According to the pre-polishing composition containing such pre-polishing abrasive grains (for example, silica abrasive grains), a high-quality surface can be realized even by a shorter finishing polishing process.
- pre-polishing composition containing such pre-polishing abrasive grains for example, silica abrasive grains
- the pre-polishing abrasive contained in the pre-polishing composition may be one kind or two or more kinds having different materials, particle shapes or particle sizes.
- the abrasive grains for preliminary polishing for example, 70% by weight or more, preferably 80% by weight or more, more preferably 90 wt% or more, more preferably 95 wt% or more, particularly preferably 99 wt% or more can be used as one kind of silica abrasive grains or alumina abrasive grains.
- a pre-polishing composition in which the pre-polishing abrasive grains are one kind of silica abrasive grains or one kind of alumina abrasive grains may be used.
- the pre-polishing composition in which the pre-polishing abrasive grains are composed of one type of silica abrasive grains (for example, colloidal silica) the surface roughness in the pre-polishing process is suppressed, and a high-quality surface is more efficiently used in the final polishing process. It can be realized.
- the concentration of the pre-polishing abrasive is not particularly limited, and can be, for example, 0.1% by weight or more, 0.5% by weight, or 1% by weight or more.
- the concentration of the pre-polishing abrasive grains can be 50% by weight or less, 40% by weight or less, 35% by weight or less, or 30% by weight or less.
- the concentration of the pre-polishing abrasive grains may be, for example, 5% by weight or more, 12% by weight or more, 17% by weight or more, or 22% by weight or more. As the concentration of the pre-polishing abrasive increases, the polishing efficiency tends to improve.
- the concentration can be preferably applied, for example, in an embodiment in which the pre-polishing abrasive grains are composed of silica abrasive grains, or 70% by weight or more of the pre-polishing abrasive grains are composed of silica abrasive grains.
- the preliminary polishing composition may contain one or more of any of the acids described above as an optional component.
- an acid By using an acid, the pH of the preliminary polishing composition can be adjusted. For example, when the pH of the preliminary polishing composition is set to less than 2.0, less than 1.5, or less than 1.0 using an acid, high polishing efficiency is easily obtained.
- the acid is preferably a strong acid, specifically having a pKa of less than 1, more preferably having a pKa of less than 0.5, and even more preferably having a pKa of less than 0.
- oxo acid is preferable.
- strong acids that can be used in the preliminary polishing composition include hydrochloric acid, sulfuric acid, and nitric acid.
- the acid concentration in the preliminary polishing composition can be appropriately selected from the acid concentrations described above.
- the preliminary polishing composition can contain one or more oxidizing agents as optional components.
- the oxidizing agent can be useful for improving the polishing efficiency and reducing the surface roughness in the preliminary polishing step.
- Specific examples of the oxidizing agent used in the preliminary polishing composition include hydrogen peroxide; nitrate compounds, for example, nitrates such as iron nitrate, silver nitrate, and aluminum nitrate; nitrate complexes such as cerium ammonium nitrate;
- persulfate metal salts such as sodium persulfate and potassium persulfate and persulfates such as ammonium persulfate; chlorate compounds or perchlorate compounds such as perchlorate and chlorate such as potassium perchlorate Bromate compounds such as bromate salts such as potassium bromate; iodate compounds such as iodate such as ammonium iodate; periodate compounds such as periodate such as sodium periodate; dichloroisocyanuric Dichloroiso
- the preliminary polishing composition includes a composite metal oxide as an oxidizing agent.
- the composite metal oxides include metal nitrates, ferric acid compounds, permanganic acid compounds, chromic acid compounds, vanadic acid compounds, ruthenium acid compounds, molybdate compounds, rhenic acid compounds, tungstic acid. Compounds. Permanganic acid compounds, vanadic acid compounds, iron acid compounds, and chromic acid compounds are more preferable, and permanganic acid compounds and vanadic acid compounds are more preferable.
- the preliminary polishing composition may or may not contain an oxidizing agent other than the composite metal oxide.
- the technique disclosed herein can be preferably implemented in a mode in which the preliminary polishing composition does not substantially contain an oxidizing agent (for example, hydrogen peroxide or persulfate) other than the composite metal oxide as an oxidizing agent.
- the preliminary polishing composition may contain other oxidizing agent such as hydrogen peroxide or persulfate in addition to the complex metal acid.
- the concentration of the oxidizing agent is not particularly limited.
- the concentration of the oxidizing agent is usually suitably 0.01% by weight or more, and may be 0.05% by weight or more, 0.1% by weight or more, 0.5% by weight or more, or 1.0% by weight. That's all.
- the concentration of the oxidizing agent is usually suitably 5.0% by weight or less, may be 3.0% by weight or less, 2.5% by weight or less, 1.5% by weight or less, 1.0% It may be not more than wt%, not more than 0.5 wt%, or not more than 0.3 wt%.
- the pH of the preliminary polishing composition is not particularly limited, and can be selected from a range of about 0.5 to 12, for example.
- the pH of the preliminary polishing composition can be selected in consideration of the composition of other components contained in the preliminary polishing composition.
- the pre-polishing composition can be acidic with a pH of less than 7.0.
- the pH of the preliminary polishing composition may be less than 5.0, less than 3.0, or less than 2.5.
- the pH of the preliminary polishing composition is preferably less than 2.0, less than 1.5 or less than 1.2.
- the polishing efficiency tends to be improved by using a lower pH pre-polishing composition. After polishing with such a strongly acidic pre-polishing composition, by performing final polishing using the polishing composition disclosed herein, a high-quality surface can be efficiently obtained.
- the pH of the preliminary polishing composition is less than 5.0, the preliminary polishing composition may contain an oxidizing agent or may not contain an oxidizing agent.
- a preliminary polishing composition having a pH of less than 2.0 and containing at least hydrogen peroxide can be preferably used.
- the pre-polishing composition having a pH of less than 5.0 contains an oxidizing agent, for example, a persulfate metal salt can be used as the oxidizing agent.
- the pre-polishing composition may be a composition having a pH of less than 5.0 or less than 3.0 and containing a metal persulfate and no hydrogen peroxide.
- the pH of the preliminary polishing composition may be, for example, 5.0 or more, 5.5 or more, or 6.0 or more. Further, the pH of the preliminary polishing composition may be, for example, 10 or less, or 8.0 or less.
- the preliminary polishing composition having a weakly acidic to weakly alkaline liquid property has an advantage of good handleability.
- the preliminary polishing composition having liquid properties preferably contains an oxidizing agent. After polishing with a pre-polishing composition having a weak acidity to weak alkalinity and containing an oxidizer, by performing final polishing using the polishing composition disclosed herein, a high-quality surface is efficiently obtained. Obtainable.
- the pH of the preliminary polishing composition is 5.0 or more, the preliminary polishing composition may or may not contain an acid.
- a preliminary polishing composition having a pH of 5.5 or higher and containing at least no strong acid can be preferably used.
- the preliminary polishing composition can contain the compound Cpho described above as an optional component.
- the relative relationship between the concentration wp [wt%] of the compound C pho in the preliminary polishing composition and the concentration w1 [wt%] of the compound C pho in the final polishing composition is not particularly limited.
- wp ⁇ w1 may be sufficient, wp> w1 may be sufficient, and wp and w1 may be comparable.
- the concentration is preferably set so that wp ⁇ w1.
- wp may be 3/4 or less of w1, 2/3 or less, 1/2 or less, 1/5 or less, or 1/10 or less.
- the pre-polishing composition according to a preferred embodiment does not contain the compound Cpho . In this case, wp is zero.
- Pre-polishing and final polishing can be applied to both polishing using a single-side polishing apparatus and polishing using a double-side polishing apparatus.
- the object to be polished is affixed to the ceramic plate with wax, or the object to be polished is held using a holder called a carrier, and the polishing pad is pressed against one side of the object to be polished while supplying the polishing composition. Then, one side of the object to be polished is polished by relatively moving both of them (for example, rotational movement).
- a polishing object is held using a holder called a carrier, and while supplying a polishing composition from above, a polishing pad is pressed against the opposite surface of the polishing object and rotated in a relative direction.
- a polishing pad is pressed against the opposite surface of the polishing object and rotated in a relative direction.
- the polishing pad used for polishing in each of the preliminary polishing step and the final polishing step is not particularly limited. For example, any one having high hardness, low hardness, including abrasive grains, or not including abrasive grains may be used. It is preferable to use a polishing pad that does not contain abrasive grains at least in the second polishing step. For example, it is preferable to use a polishing pad that does not contain abrasive grains in both the first and second polishing steps.
- a high hardness is a polishing pad having an Asker C hardness higher than 80
- a low hardness is a polishing pad having an Asker C hardness of 80 or less.
- the polishing pad with high hardness is, for example, a hard foam polyurethane type or a nonwoven fabric type polishing pad.
- the polishing pad with low hardness is preferably a polishing pad in which at least the side pressed against the object to be polished is made of a soft foamed resin such as soft foamed polyurethane, for example, a suede type polishing pad.
- the suede type polishing pad is typically made of soft foamed polyurethane on the side pressed against the object to be polished.
- Asker C hardness can be measured using Asker rubber hardness meter C type manufactured by Asker. Polishing with the polishing composition disclosed herein can be preferably performed using, for example, a suede type polishing pad. In particular, it is preferable to use a suede type polishing pad in the final polishing step.
- the polished product polished by the method disclosed herein is typically washed after polishing. This washing can be performed using an appropriate washing solution.
- the cleaning liquid to be used is not particularly limited, and a known and commonly used cleaning liquid can be appropriately selected and used.
- the polishing method disclosed herein may include any other process in addition to the preliminary polishing process and the final polishing process.
- An example of such a process is a lapping process performed before the preliminary polishing process.
- the lapping step is a step of polishing the polishing object by pressing the surface of the polishing surface plate (for example, cast iron surface plate) against the polishing object. Therefore, no polishing pad is used in the lapping process.
- the lapping process is typically performed by supplying abrasive grains (typically diamond abrasive grains) between the polishing surface plate and the object to be polished.
- the polishing method disclosed herein may include an additional step (a cleaning step or a polishing step) before the preliminary polishing step or between the preliminary polishing step and the final polishing step.
- the technique disclosed herein includes a method for producing a polished article (for example, a method for producing a gallium nitride substrate or a gallium oxide substrate) including a polishing step using the polishing composition, and a polished article produced by the method. Offerings may be included. That is, according to the technique disclosed herein, the method includes supplying a polishing composition disclosed herein to a polishing object composed of a material to be polished and polishing the polishing object. A method for producing an abrasive and an abrasive produced by the method are provided. The above manufacturing method can be implemented by preferably applying the contents of any of the polishing methods disclosed herein. According to the above manufacturing method, a polished product (for example, a gallium nitride substrate, a gallium oxide substrate, etc.) having a high-quality surface can be efficiently provided.
- a polished product for example, a gallium nitride substrate, a gallium oxide substrate, etc.
- the polishing method disclosed herein is typically applied to a polishing process for a gallium compound semiconductor substrate (hereinafter also simply referred to as “substrate”). Before the first polishing step, the substrate may be subjected to a general process that can be applied to the gallium compound semiconductor substrate in a process upstream of the polishing process, such as grinding (grinding) or lapping. Good.
- the slurry used in the polishing method disclosed herein will be described in the order of the slurry S2 used in the second polishing step and the slurry S1 used in the first polishing step.
- the slurry S2 in the technique disclosed herein includes abrasive grains A2, water, and a compound Cpho .
- the slurry S2 in the technology disclosed herein includes abrasive grains A2.
- abrasive grain A2 the thing similar to the abrasive grain contained in the polishing composition mentioned above can be used preferably.
- concentration of the abrasive grain A2 in slurry S2 is not specifically limited, It can be set as the density
- the slurry S2 contains water as an essential component.
- the same water as that contained in the above-described polishing composition can be preferably used.
- the slurry S2 in the technique disclosed herein contains a compound Cpho having a phosphate group or a phosphonic acid group as an essential component.
- a compound Cpho having a phosphate group or a phosphonic acid group as an essential component.
- the compound C pho contained in the slurry S2 it may be preferably used those similar to compounds C pho contained in the polishing composition as defined above.
- the concentration [wt%] of the compound C pho in the slurry S2 is not particularly limited, but may be the same concentration as the concentration of the compound C pho in the polishing composition described above.
- the slurry S2 in the technique disclosed herein preferably does not contain an oxidant or the concentration of the oxidant is not more than a predetermined value from the viewpoint of better exhibiting the surface quality improvement effect by the compound Cpho .
- the concentration of the oxidizing agent in the slurry S2 is preferably less than 0.1% by weight, more preferably less than 0.05% by weight, still more preferably less than 0.02% by weight, particularly preferably less than 0.01% by weight. It is.
- the oxidizing agent can be selected from the same oxidizing agents that can be used for the slurry S1 described later.
- the oxidizing agent contained in the slurry S1 and the oxidizing agent contained in the slurry S2 may be the same or different.
- the technique disclosed here can be preferably implemented using the slurry S2 containing no oxidizing agent.
- the slurry S2 having such a composition the effect of improving the surface quality by the compound Cpho tends to be exhibited particularly well. Therefore, a surface having a low surface roughness Ra and a suppressed pit generation can be effectively realized.
- the oxidizing agents it is particularly preferable to use a slurry S2 that does not contain any of hydrogen peroxide, sodium persulfate, potassium persulfate, ammonium persulfate, and sodium dichloroisocyanurate.
- the fact that the polishing composition (slurry) does not contain an oxidant means that at least intentionally no oxidant is blended, and a trace amount of oxidant derived from raw materials, production methods, and the like. Is inevitably included.
- the trace amount means that the molar concentration of the oxidizing agent in the polishing composition is 0.0005 mol / L or less (preferably 0.0001 mol / L or less, more preferably 0.00001 mol / L or less, particularly preferably 0.00. 00000 mol / L or less).
- the content of the oxidizing agent is preferably zero or below the detection limit.
- the pH of the slurry S2 can be in the same range as the pH of the polishing composition described above.
- the slurry S2 may contain one or two or more acids as optional components used for the purpose of adjusting pH, etc., if necessary, in addition to the essential components of abrasive grains, water, and compound Cpho . Acids corresponding to the compound Cpho , that is, phosphoric acid, phosphorous acid, and phosphonic acid are not included in the examples of acids mentioned here.
- the acid that can be contained in the slurry S2 the same acid that can be contained in the polishing composition described above can be preferably used.
- the concentration of the acid is not particularly limited, but may be the same concentration as the acid that can be contained in the polishing composition described above.
- the total of the concentration w1 [wt%] of the compound Cpho in the slurry S2 and the concentration w2 [wt%] of the acid (preferably strong acid) is the concentration of the compound Cpho in the polishing composition described above. It can be set to the same range as the sum of w1 [wt%] and acid (preferably strong acid) concentration w2 [wt%].
- the slurry S2 contains a combination of the compound Cpho and an acid (preferably a strong acid)
- the relationship between the content m1 [mol / kg] of the compound Cpho and the content m2 [mol / kg] of the acid is described above. It can set similarly to content of compound Cpho and an acid (preferably strong acid) in polishing composition. If the slurry S2 is compound C pho and acid (preferably a strong acid) belonging to the (C) in combination and the content of compound C pho above (C) M1c [mol / kg], the composition for polishing the above-mentioned it can be the same as content m1C compound C pho above (C) in the object.
- the composition for polishing the above-mentioned it can be the same as content m1A compound C pho above (a) in the object.
- Such above relationship between the compound C pho content m1A and acid content m2 of (A) contains the slurry S2 is combined with the above (B) compounds belonging to C pho and acid (preferably a strong acid) relationships and the content m2 content m1B and acid compound C pho above (B) in the case, if the slurry S2 is (preferably a strong acid) compound C pho and acid belonging to the (D) in combination with the It may be preferably applied to the relationship between the content m2 content m1D and acid compound C pho (D) above in.
- Slurry S2 is a chelating agent, thickener, dispersant, surface protective agent, wetting agent, organic or inorganic base, surfactant, rust preventive, antiseptic, antifungal, as long as the effects of the present invention are not impaired.
- a known additive that can be used for a polishing composition typically a composition for polishing a high-hardness material, such as a composition for polishing a gallium nitride substrate), such as an agent, may be further contained as necessary. .
- the method for producing the slurry S2 is not particularly limited.
- each component contained in the slurry S2 may be mixed using a well-known mixing device such as a blade-type stirrer, an ultrasonic disperser, or a homomixer.
- the aspect which mixes these components is not specifically limited, For example, all the components may be mixed at once and may be mixed in the order set suitably. The same applies to the slurry S1.
- the slurry S2 may be in a concentrated form (that is, in the form of a polishing liquid concentrate) before being supplied to the object to be polished.
- the polishing composition in such a concentrated form is advantageous from the viewpoints of convenience, cost reduction, and the like during production, distribution, storage, and the like of the polishing composition.
- the concentration rate can be, for example, about 1.2 to 5 times in terms of volume.
- the polishing composition in the form of a concentrated liquid can be used in such a mode that a polishing liquid is prepared by diluting at a desired timing and the polishing liquid is supplied to a polishing object.
- the dilution can be typically performed by adding the aforementioned solvent to the concentrated solution and mixing.
- the said solvent when the said solvent is a mixed solvent, you may add and dilute only some components among the structural components of this solvent, and add the mixed solvent which contains those structural components in the amount ratio different from the said solvent. May be diluted.
- some of these agents may be diluted and then mixed with other agents to prepare a polishing liquid. After mixing a plurality of agents, the mixture is diluted. A polishing liquid may be prepared. The same applies to the slurry S1.
- the slurry S1 used in the first polishing step includes abrasive grains A1 and water.
- slurry S1 the thing similar to the composition for preliminary polishing mentioned above can be used preferably.
- water the same water as in the slurry S2 can be preferably used.
- the material and properties of the abrasive grain A1 are not particularly limited.
- materials that can be used as the abrasive grain A1 include silica particles, alumina, cerium oxide, chromium oxide, titanium dioxide, zirconium oxide, magnesium oxide, manganese dioxide, zinc oxide, iron oxide, and the like; silicon nitride, nitriding Abrasive grains substantially composed of any one of nitrides such as boron; carbides such as silicon carbide and boron carbide; diamonds; carbonates such as calcium carbonate and barium carbonate; Among these, abrasive grains substantially composed of oxides such as silica, alumina, cerium oxide, chromium oxide, zirconium oxide, manganese dioxide, and iron oxide are preferable because they can form a good surface.
- silica abrasive grains, alumina abrasive grains, and zirconium oxide abrasive grains are more preferable, and silica abrasive grains and alumina abrasive grains are particularly preferable.
- the silica abrasive grains used for the abrasive grains A1 can be appropriately selected from the materials exemplified above as the silica abrasive grains that can be used for the slurry S2.
- the silica abrasive grains used as the abrasive grains A1 and the silica abrasive grains used as the abrasive grains A2 may have the same particle diameter or shape, or one or both of the particle diameter and shape may be different from each other. .
- the alumina abrasive grains used for the abrasive grain A1 can be appropriately selected from known alumina particles.
- known alumina particles include ⁇ -alumina and intermediate alumina.
- intermediate alumina is a general term for alumina particles other than ⁇ -alumina, and specific examples include ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, and ⁇ -alumina. Is done.
- alumina called fumed alumina typically alumina fine particles produced when high-temperature firing of an alumina salt
- fumed alumina may be used based on classification according to the production method.
- alumina referred to as alumina hydrate such as boehmite
- colloidal alumina or alumina sol is also included in the examples of the known alumina particles.
- ⁇ -alumina is particularly preferable.
- the average secondary particle diameter of the abrasive grains A1 contained in the slurry S1 is usually 20 nm or more, and preferably 35 nm or more, more preferably 50 nm or more, and 60 nm or more from the viewpoint of polishing efficiency. Further, from the viewpoint of easily improving the surface quality in the second polishing step, the average secondary particle diameter of the abrasive grains A1 is usually appropriately 2000 nm or less, preferably 1000 nm or less, 800 nm or less, or 600 nm or less. .
- the average secondary particle diameter of the abrasive grains A1 is preferably 100 nm or more, more preferably 200 nm or more, and may be 300 nm or more or 400 nm or more. According to the abrasive grains A1 (for example, alumina abrasive grains) having such an average secondary particle diameter, high polishing efficiency is easily obtained in the first polishing step. In some embodiments, the average secondary particle diameter of the abrasive grains A1 is preferably 300 nm or less, more preferably 200 nm or less, and may be 150 nm or less, 100 nm or less, or 80 nm or less. According to the abrasive grains A1 (for example, silica abrasive grains) having such an average secondary particle diameter, a high-quality surface can be realized even in a shorter second polishing step.
- abrasive grain A1 contained in slurry S1 the thing similar to the abrasive grain contained in the composition for preliminary
- concentration of abrasive grain A1 in slurry S1 is not specifically limited, It can be made to be the same as the density
- the concentration of the abrasive grains A1 in the slurry S1 may be, for example, 20% by weight or less, 15% by weight or less, or 10% by weight or less. It may be less than wt%.
- the concentration can be preferably applied in, for example, an aspect in which the abrasive grains A1 are made of abrasive grains that are harder than silica abrasive grains, or an aspect in which 70% by weight or more of the abrasive grains A1 are made of abrasive grains with high hardness.
- the high-hardness abrasive grains include alumina abrasive grains and zirconium oxide abrasive grains.
- the slurry S1 can contain one or more acids as optional components.
- the pH of the slurry S1 can be adjusted by using an acid. For example, when the pH of the slurry S1 is less than 2.0, less than 1.5, or less than 1.0 using an acid, high polishing efficiency is easily obtained.
- the acid used for the slurry S1 can be appropriately selected from the materials exemplified above as the acid that can be used for the polishing composition (or the slurry S2).
- the acid concentration can be appropriately selected from a range similar to the acid concentration in the polishing composition (or slurry S2) described above.
- the slurry S1 may contain one or more oxidizing agents as optional components. By containing an oxidizing agent in the slurry S1, the slurry S1 can effectively act on the surface of the object to be polished. Therefore, inclusion of an oxidizing agent in the slurry S1 can be useful for improving polishing efficiency and reducing surface roughness.
- Specific examples of the oxidizing agent used in the slurry S1 include hydrogen peroxide; nitrate compounds such as nitrates such as iron nitrate, silver nitrate, and aluminum nitrate; nitrate complexes such as cerium ammonium nitrate; persulfate compounds such as persulfuric acid.
- Persulfate metal salts such as sodium and potassium persulfate and persulfates such as ammonium persulfate; Perchlorates and chlorates such as chlorate compounds or perchlorate compounds such as potassium perchlorate; Bromate Compounds, eg bromates such as potassium bromate; iodate compounds, eg iodates such as ammonium iodate; periodate compounds, eg periodate such as sodium periodate; sodium dichloroisocyanurate, Dichloroisocyanurate such as potassium dichloroisocyanurate; iron acid compounds, for example, iron salts such as potassium ferrate; Manganic acid compounds such as permanganate such as sodium permanganate and potassium permanganate; Chromate compounds such as chromate such as potassium chromate and potassium dichromate; Vanadate compounds such as metavanadate Metavanadates such as ammonium, sodium metavanadate and potassium metavanadate; perruthenic acid compounds such as perruthenate;
- the slurry S1 includes a composite metal oxide as an oxidizing agent.
- the composite metal oxides include metal nitrates, ferric acid compounds, permanganic acid compounds, chromic acid compounds, vanadic acid compounds, ruthenium acid compounds, molybdate compounds, rhenic acid compounds, tungstic acid. Compounds. Permanganic acid compounds, vanadic acid compounds, iron acid compounds, and chromic acid compounds are more preferable, and permanganic acid compounds and vanadic acid compounds are more preferable.
- the slurry S1 includes, as the composite metal oxide, a monovalent or divalent metal element (excluding a transition metal element), and a fourth periodic transition metal element in the periodic table.
- the mixed metal oxide is used.
- the monovalent or divalent metal element include Na, K, Mg, and Ca. Of these, Na and K are more preferable.
- the fourth periodic transition metal element in the periodic table include Fe, Mn, Cr, V, and Ti. Among these, Mn, V, Fe, and Cr are more preferable, and Mn and V are more preferable.
- the slurry S1 may or may not contain an oxidant other than the composite metal oxide.
- the technique disclosed here can be preferably implemented in a mode in which the slurry S1 does not substantially contain an oxidizing agent (for example, hydrogen peroxide or persulfate) other than the composite metal oxide as an oxidizing agent.
- slurry S1 may contain other oxidizing agents, for example, hydrogen peroxide and persulfate, in addition to the above-mentioned complex metal acid.
- the concentration of the oxidizing agent is not particularly limited.
- the concentration of the oxidizing agent is usually suitably 0.01% by weight or more, preferably 0.05% by weight or more.
- the oxidizing agent concentration of the slurry S1 may be, for example, 0.1% by weight or more, 0.5% by weight or more, or 1.0% by weight or more.
- the concentration of the oxidizing agent is usually suitably 5.0% by weight or less, and preferably 3.0% by weight or less.
- the oxidant concentration of the slurry S1 may be, for example, 2.5 wt% or less, may be 1.5 wt% or less, 1.0 wt% or less, 0.5 wt% or less, or 0 It may be 3% by weight or less.
- the pH of the slurry S1 is not particularly limited, and can be selected from a range of about 0.5 to 12, for example.
- the pH of the slurry S1 can be selected in consideration of the composition of other components contained in the slurry S1.
- the slurry S1 can be acidic with a pH of less than 7.0.
- the pH of the slurry S1 may be less than 5.0, less than 3.0, or less than 2.5.
- the pH of the slurry S1 is preferably less than 2.0, less than 1.5 or less than 1.2.
- the slurry S1 may contain an oxidizing agent or may not contain an oxidizing agent.
- a slurry S1 having a pH of less than 2.0 and containing at least hydrogen peroxide can be preferably used.
- a persulfate metal salt can be used as the oxidizing agent.
- the slurry S1 may have a composition that is less than pH 5.0 or less than pH 3.0, contains a metal persulfate, and does not contain hydrogen peroxide.
- the pH of the slurry S1 may be, for example, 5.0 or more, 5.5 or more, or 6.0 or more. Further, the pH of the slurry S1 may be 10 or less, for example, or 8.0 or less.
- the liquid S1 preferably contains an oxidizing agent.
- the slurry S1 may or may not contain an acid.
- a slurry S1 having a pH of 5.5 or higher and containing at least no strong acid can be preferably used.
- the slurry S1 can contain a compound Cpho having a phosphoric acid group or a phosphonic acid group as an optional component. By containing the compound Cpho in the slurry S1, the effect of suppressing surface roughness in the first polishing step can be exhibited. If the slurry S1 contains a compound C pho, the compound C pho may be selected from those similar to the compound C pho that may be used in the slurry S2. In embodiments the slurry S1, S2 is containing a compound C pho both, the compound C pho contained in the slurry S1, and the compound C pho contained in the slurry S2, may be the same or may be different.
- concentration [wt%] of Compound C pho in the slurry S1 is, it is preferable to lower than the concentration of the compound C pho in the slurry S2 w1 [wt%].
- concentration [wt%] of the compound Cpho in the slurry S1 may be expressed as wp. If wp is greater than or equal to w1, the efficiency of the entire multistage polishing process including the first and second polishing steps tends to decrease, and the total polishing time required to obtain a high-quality surface tends to increase.
- the concentration wp [wt%] of the compound C pho in case of incorporating the compound C pho the slurry S1 is against the concentration of compound C pho in the slurry S2 w1 [wt%], the 3/4 2/3 or less, 1/2 or less, 1/5 or less, or 1/10 or less.
- the total polishing time means the total of the polishing time in the first polishing step and the polishing time in the second polishing step. Therefore, for example, the time from the end of polishing in the first polishing step to the start of polishing in the second polishing step is not included in the total polishing time.
- the concentration wp [wt%] of the compound C pho in the slurry S1 may be, for example, 0.01 wt% or more, 0.1 wt% or more, 0.5 wt% or more, or 1 wt% or more. Good.
- wp is preferably set to be less than 5.0% by weight, less than 4.0% by weight, or less than 3.0% by weight, and lower than w1.
- the technique disclosed here can also be preferably implemented in an embodiment in which the slurry S1 does not contain the compound Cpho .
- Slurry S1 is a chelating agent, thickener, dispersant, surface protective agent, wetting agent, organic or inorganic base, surfactant, rust preventive, antiseptic, antifungal as long as the effects of the present invention are not impaired.
- a known additive that can be used for a polishing composition typically a composition for polishing a high-hardness material, such as a composition for polishing a gallium nitride substrate), such as an agent, may be further contained as necessary. .
- the technology disclosed herein can include, for example, providing the following polishing composition set. That is, according to the technique disclosed herein, a polishing composition set including the composition Q1 and the composition Q2 stored separately from each other is provided.
- the composition Q1 may be the slurry S1 used in the first polishing step in the polishing method disclosed herein or a concentrated solution thereof.
- the composition Q2 may be the slurry S2 used in the second polishing step in the polishing method disclosed herein or a concentrated solution thereof.
- the polishing composition set having such a configuration in a multistage polishing process including the first and second polishing steps, high polishing efficiency and a high-quality surface after polishing can be suitably achieved.
- the polishing method disclosed herein includes a first polishing step and a second polishing step in this order.
- polishing process is a process of grind
- polishing process is a process of further grind
- a first polishing liquid containing any of the slurries S1 disclosed herein, that is, a polishing liquid to be supplied to the object to be polished in the polishing in the first polishing step is prepared.
- polishing process is prepared.
- Preparing the polishing liquid includes using each slurry as a polishing liquid as it is, or preparing a polishing liquid by adding operations such as concentration adjustment (for example, dilution) and pH adjustment to each slurry. May be included.
- the first polishing process is performed using the prepared first polishing liquid.
- the first polishing liquid is supplied to the surface of the gallium compound semiconductor substrate, which is an object to be polished, and is polished by a conventional method.
- the polishing object that has undergone the lapping process is set in a general polishing apparatus, and the first polishing liquid is supplied to the surface of the polishing object through the polishing pad of the polishing apparatus.
- the polishing pad is pressed against the surface of the object to be polished to relatively move (for example, rotate) the two.
- a second polishing step is performed using the prepared second polishing liquid.
- the second polishing liquid is supplied to the gallium compound semiconductor substrate that is the object to be polished, and polishing is performed by a conventional method.
- the second polishing step is performed by supplying the second polishing liquid to the surface of the object to be polished after finishing the first polishing step through the polishing pad of the polishing apparatus.
- the polishing pad is pressed against the surface of the object to be polished, and both are relatively moved (for example, rotated).
- the polishing of the gallium compound semiconductor substrate is completed through the above polishing process.
- the first polishing step is a polishing step performed by supplying a polishing composition (slurry) containing abrasive grains and water between a polishing pad and an object to be polished. It means a polishing process performed before the polishing process. In a typical embodiment, the first polishing process is a polishing process arranged immediately before the second polishing process.
- the first polishing step may be a one-step polishing step or a multi-step polishing step of two or more steps.
- the second polishing step is the last (that is, the most downstream) of the polishing steps performed by supplying a polishing composition containing abrasive grains and water between the polishing pad and the object to be polished.
- the slurry S2 in the technique disclosed herein is used on the most downstream side of the polishing composition used in the polishing process of the gallium compound semiconductor substrate. It can be understood as a kind of polishing composition.
- the polishing conditions in each polishing step are appropriately set based on the technical common knowledge of those skilled in the art in view of the polishing object, target surface quality (for example, surface roughness), polishing efficiency, and the like.
- target surface quality for example, surface roughness
- polishing efficiency the polishing pressure per 1 cm 2 of the processing area of the object to be polished is preferably 50 g or more, more preferably 100 g or more.
- the polishing pressure per processing area of 1 cm 2 is 1000 g or less.
- the linear velocity can generally vary due to the influence of the platen rotation speed, the carrier rotation speed, the size of the polishing object, the number of polishing objects, and the like. Higher polishing efficiency tends to be obtained by increasing the linear velocity. Further, from the viewpoint of preventing damage to the polishing object and excessive heat generation, the linear velocity can be limited to a predetermined value or less.
- the linear velocity is not particularly limited as long as it is set based on common general technical knowledge, but is preferably in the range of about 0.1 to 20 m / second, and more preferably in the range of 0.5 to 5 m / second.
- the supply amount of the polishing liquid at the time of polishing is not particularly limited.
- the supply amount is desirably set so as to be a sufficient amount to supply the polishing liquid to the entire surface of the object to be polished without unevenness.
- a suitable supply amount may vary depending on the material of the object to be polished, the configuration of the polishing apparatus, and other conditions. For example, it is preferably in the range of 0.001 to 0.1 mL / min, more preferably in the range of 0.003 to 0.03 mL / min per 1 mm 2 processed area of the polishing object.
- the total polishing time in the polishing method disclosed herein (that is, the sum of the polishing time of the first polishing step and the polishing time of the second polishing step) is not particularly limited.
- a high-quality surface can be realized with a total polishing time of, for example, 10 hours or less for GaN and other gallium compound semiconductor substrates.
- a high-quality surface can be achieved for GaN and other gallium compound semiconductor substrates with a total polishing time of 8 hours or less, and more preferably 6 hours or less.
- Each of the first and second polishing steps can be applied to either a single-side polishing apparatus or a double-side polishing apparatus.
- a polishing object is affixed to a ceramic plate with wax, or a polishing object is held using a holder called a carrier, and a polishing pad is pressed against one side of the polishing object while supplying a polishing composition. Then, one side of the object to be polished is polished by relatively moving both of them (for example, rotational movement).
- a polishing object is held by using a holder called a carrier, and a polishing pad is pressed against the opposite surface of the polishing object while supplying a polishing composition from above, and these are rotated in a relative direction.
- a polishing pad is pressed against the opposite surface of the polishing object while supplying a polishing composition from above, and these are rotated in a relative direction.
- the polishing pad used for each polishing step is not particularly limited. For example, any one having high hardness, low hardness, including abrasive grains, or not including abrasive grains may be used.
- a high hardness is a polishing pad having an Asker C hardness higher than 80
- a low hardness is a polishing pad having an Asker C hardness of 80 or less.
- the polishing pad with high hardness is, for example, a hard foam polyurethane type or a nonwoven fabric type polishing pad.
- the polishing pad with low hardness is preferably a polishing pad in which at least the side pressed against the object to be polished is made of a soft foamed resin such as soft foamed polyurethane, for example, a suede type polishing pad.
- the suede type polishing pad is typically made of soft foamed polyurethane on the side pressed against the object to be polished.
- Asker C hardness can be measured using Asker rubber hardness meter C type manufactured by Asker.
- the polishing method disclosed herein can be preferably carried out in an embodiment using a polishing pad that does not contain abrasive grains at least in the second polishing step. For example, it is preferable to use a polishing pad that does not contain abrasive grains in both the first and second polishing steps.
- Examples of the polishing pad that can be preferably used in the second polishing step include a polishing pad having a surface made of soft polyurethane foam, that is, a polishing pad configured to be used by pressing the surface made of soft polyurethane foam against an object to be polished.
- a polishing pad having a surface made of soft foamed polyurethane includes a pad made entirely of soft foamed polyurethane, or a pad base material (also called a base base material) such as a nonwoven fabric or a polyethylene terephthalate (PET) film. .))
- PET polyethylene terephthalate
- a so-called suede type polishing pad having a soft foamed polyurethane layer produced by a wet film forming method on a base substrate By performing the second polishing step using a suede type polishing pad, a higher quality surface (for example, a smaller surface roughness Ra) tends to be obtained.
- a polishing pad having a structure in which polyurethane is impregnated with a nonwoven fabric is not included in the concept of the polishing pad having the surface made of the soft foam polyurethane.
- the suede pad can be preferably used in the first polishing step.
- the first polishing step can be preferably carried out using a hard foam polyurethane type polishing pad or a non-woven type polishing pad. According to the hard foam polyurethane type or non-woven fabric type polishing pad, higher polishing efficiency tends to be obtained in the first polishing step. Thereafter, a high-quality surface can be efficiently realized by performing a second polishing step using the slurry S2 and preferably using a suede pad.
- the polished product polished by the method disclosed herein is typically washed after polishing. This washing can be performed using an appropriate washing solution.
- the cleaning liquid to be used is not particularly limited, and a known and commonly used cleaning liquid can be appropriately selected and used.
- the polishing method disclosed herein may include any other step in addition to the first polishing step and the second polishing step.
- An example of such a process is a lapping process performed before the first polishing process.
- the lapping step is a step of polishing the polishing object by pressing the surface of the polishing surface plate (for example, cast iron surface plate) against the polishing object. Therefore, no polishing pad is used in the lapping process.
- the lapping process is typically performed by supplying abrasive grains (typically diamond abrasive grains) between the polishing surface plate and the object to be polished.
- the polishing method disclosed herein may include an additional step (cleaning step or other polishing step) before the first polishing step or between the first polishing step and the second polishing step.
- the matters disclosed by this specification include a method for producing a polished article (for example, a method for producing a gallium nitride substrate or a gallium oxide substrate) including performing the above-described polishing method, and a polished article produced by the method. Offerings may be included. That is, this specification provides a method for producing a polished article and a polished article produced by the method, which include polishing any object to be polished by applying any of the polishing methods disclosed herein. According to the above manufacturing method, a polished product (for example, a gallium nitride substrate, a gallium oxide substrate, etc.) having a high-quality surface can be efficiently provided.
- a polished product for example, a gallium nitride substrate, a gallium oxide substrate, etc.
- polishing compositions having the compositions shown in Table 1 were prepared.
- silica abrasive grains spherical colloidal silica having an average secondary particle diameter (D50) of 65 nm was used.
- HEDP represents hydroxyethylidene diphosphonic acid
- EDTPO represents ethylenediaminetetra (methylenephosphonic acid)
- EAP represents ethyl acid phosphate, which correspond to compound Cpho .
- EAP used here is a mixture of monoester and diester of phosphoric acid, and the weight average molecular weight based on their weight fraction is 140.
- TTHA represents triethylenetetramine hexaacetic acid
- DTPA represents diethylenetriaminepentaacetic acid, and these do not correspond to the compound C pho because they have neither a phosphate group nor a phosphonic acid group.
- the polishing composition of Example 1-3 contained 0.6% potassium hydroxide to dissolve EDTPO, and the polishing compositions of Comparative Examples 1-3 and 1-4 were used.
- the composition contained 0.3% potassium hydroxide to dissolve TTHA and DTPA.
- the balance of the polishing composition according to each example is made of water. Table 1 also shows the pH of the polishing composition according to each example.
- polishing composition according to each example was directly used as a polishing liquid, and the (0001) plane, that is, the C plane of a commercially available non-doped (n-type) freestanding GaN wafer was polished under the following polishing conditions. All of the used GaN wafers are circular with a diameter of 2 inches.
- Polishing device One-side polishing machine manufactured by Fujikoshi Machine Industry Co., Ltd.
- Polishing pad Suede pad made of soft polyurethane foam (Fujimi Incorporated, Surfin 019-3, Asker C hardness: 58) Polishing pressure: 45kPa Polishing liquid supply rate: 20 mL / min (flowing) Average linear velocity: 1.5 m / sec Polishing time: 60 minutes
- ⁇ Pit suppression performance> Using the five AFM images obtained by measuring the surface roughness Ra, the number of pits present in each AFM image was visually counted. At this time, a circular dent defect having a diameter of 100 nm or more and a depth of 2 nm or more with respect to the reference surface was recognized as a pit. Based on the results, the pit suppression performance was evaluated at the following five levels of 0 to 4 points and shown in Table 1. The higher the score, the higher the pit suppression performance. 4 points: No pits are observed in all 5 AFM images. 3 points: A pit is confirmed in one of the five AFM images. 2 points: pits are confirmed in 2 out of 5 AFM images, or Three or more pits are confirmed in at least one AFM image. 1 point: Pit is confirmed in 3 or more of 5 AFM images, or Five or more pits are confirmed in at least one AFM image. 0 point: The surface state is rough and the number of pits cannot be counted.
- Comparative Example 1-5 by adding sodium persulfate or H 2 O 2 as an oxidizing agent to the polishing composition of Example 1-6 that does not contain an oxidizing agent at the concentrations shown in Table 2.
- a polishing composition according to 1-6 was prepared.
- the polishing composition according to Comparative Example 1-7 was further added with H 2 O 2 as an oxidizing agent at a concentration shown in Table 2 in the polishing composition of Example 1-11 containing no oxidizing agent.
- a product was prepared.
- S represents silica abrasive grains
- A represents alumina abrasive grains.
- silica abrasive spherical colloidal silica having an average secondary particle diameter (D50) of 65 nm was used.
- alumina abrasive grains ⁇ -alumina having an average secondary particle diameter (D50) of 450 nm was used.
- HEDP represents hydroxyethylidene diphosphonic acid
- EDTPO represents ethylenediaminetetra (methylenephosphonic acid), both of which correspond to the compound Cpho .
- the slurry S2 of Example 2-10 contained 0.6% potassium hydroxide in order to dissolve EDTPO.
- the remainder of the slurries S1 and S2 according to each example is made of water.
- Tables 3 and 4 also show the pH of the slurries S1 and S2 according to each example.
- polishing device Single-side polishing device manufactured by Nippon Engis Co., Ltd. Model “EJ-380IN” Polishing pad: As shown in Table 3. Polishing pressure: 30kPa Polishing liquid supply rate: 20 mL / min (flowing) Average linear velocity: 1.0 m / sec Polishing time: As shown in Table 3.
- polishing step Next, using the slurry S2 prepared above as a polishing liquid, the second polishing step was performed on the surface of the GaN wafer after the first polishing step was performed.
- the second polishing step was performed under the same polishing conditions as the first polishing step except that the polishing pad and the polishing time were as shown in Table 4. However, in Comparative Examples 2-1 to 2-4, the second polishing step was not performed.
- P1 indicates a soft foam polyurethane suede pad (Fujimi Incorporated, Surfin 019-3, Asker C hardness: 58), and “P2” indicates a hard foam polyurethane.
- Type polishing pad Asker C hardness: 97
- P3 indicates a non-woven type polishing pad (Asker C hardness: 82).
- ⁇ Surface roughness Ra> The surface roughness Ra of the polished wafer surface was measured under the following conditions. The results are shown in Tables 3 and 4.
- Evaluation device atomic force microscope (AFM) manufactured by Bruker Device model: nanoscope V Viewing angle: 10 ⁇ m square Number of measurement points per scan: 256 (points) Number of scans: 256 (books)
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Abstract
Description
ここに開示される技術は、ガリウム化合物系半導体基板を研磨対象物とする研磨に適用される。本明細書におけるガリウム化合物系半導体の概念には、窒化ガリウム(GaN)および酸化ガリウム(Ga2O3)の他、これらにおけるGaの一部が他の周期表13族元素(B、Al、In)で置換された組成を有する半導体、例えばAlGaN、GaInN、AlGaInN等が包含される。ここに開示される技術は、このようなガリウム化合物系半導体材料からなる表面を有する基板の研磨に好ましく適用され得る。上記表面、すなわち研磨対象面は、いずれか一種のガリウム化合物系半導体材料からなる表面、例えば該材料の単結晶の表面であってもよく、二種以上のガリウム化合物系半導体材料の混合物からなる表面、例えばそれらの材料の混晶の表面であってもよい。上記ガリウム化合物系半導体基板は、自立型のガリウム化合物系半導体ウェーハであってもよく、適宜の下地層の上にガリウム化合物系半導体の結晶を有するものであってもよい。そのような下地層の例としては、サファイア基板、シリコン基板、SiC基板等が挙げられる。ガリウム化合物系半導体は、導電性の付与等を目的としてドープされていてもよく、ノンドープであってもよい。 <Polishing object>
The technique disclosed here is applied to polishing using a gallium compound semiconductor substrate as an object to be polished. The concept of the gallium compound semiconductor in this specification includes, in addition to gallium nitride (GaN) and gallium oxide (Ga 2 O 3 ), a part of Ga in these is another group 13 element of the periodic table (B, Al, In ), For example, AlGaN, GaInN, AlGaInN, and the like. The technique disclosed herein can be preferably applied to polishing of a substrate having a surface made of such a gallium compound semiconductor material. The surface, that is, the surface to be polished may be a surface made of any one type of gallium compound semiconductor material, for example, a surface of a single crystal of the material, or a surface made of a mixture of two or more types of gallium compound semiconductor materials. For example, the surface of a mixed crystal of these materials may be used. The gallium compound semiconductor substrate may be a self-supporting gallium compound semiconductor wafer, or may have a gallium compound semiconductor crystal on an appropriate underlayer. Examples of such an underlayer include a sapphire substrate, a silicon substrate, a SiC substrate, and the like. The gallium compound semiconductor may be doped for the purpose of imparting conductivity or the like, or may be non-doped.
(砥粒)
ここに開示される研磨用組成物は、砥粒を含有する。砥粒を含む研磨用組成物を用いた研磨によると、砥粒等の固形粒子を含まない溶液による化学エッチングに比べて、例えばラッピング等の前工程において研磨対象物に生じた傷をより効率よく除去し得る。また、ここに開示される研磨用組成物によると、該組成物が後述する化合物Cphoを含むことにより、研磨による表面の荒れを抑制しつつ上記傷を効率よく除去することができる。 <Polishing composition>
(Abrasive grains)
The polishing composition disclosed herein contains abrasive grains. According to polishing using a polishing composition containing abrasive grains, for example, scratches generated on a polishing object in a previous process such as lapping can be more efficiently compared to chemical etching using a solution that does not contain solid particles such as abrasive grains. Can be removed. In addition, according to the polishing composition disclosed herein, the scratches can be efficiently removed while suppressing surface roughness due to polishing by including the compound Cpho described later.
ここに開示される研磨用組成物は、必須成分として水を含む。水としては、イオン交換水(脱イオン水)、純水、超純水、蒸留水等を好ましく用いることができる。ここに開示される研磨用組成物は、必要に応じて、水と均一に混合し得る有機溶剤(低級アルコール、低級ケトン等)をさらに含有してもよい。通常は、研磨用組成物に含まれる溶媒の90体積%以上が水であることが好ましく、95体積%以上(典型的には99~100体積%)が水であることがより好ましい。 (water)
The polishing composition disclosed herein contains water as an essential component. As water, ion exchange water (deionized water), pure water, ultrapure water, distilled water and the like can be preferably used. The polishing composition disclosed herein may further contain an organic solvent (lower alcohol, lower ketone, etc.) that can be uniformly mixed with water, if necessary. Usually, 90% by volume or more of the solvent contained in the polishing composition is preferably water, and more preferably 95% by volume or more (typically 99 to 100% by volume) is water.
ここに開示される研磨用組成物は、リン酸基またはホスホン酸基を有する化合物Cphoを、必須成分として含有する。砥粒を含む研磨用組成物に化合物Cphoを含有させることにより、研磨による研磨対象物表面の荒れを抑制し、研磨後の面品質を改善することができる。これにより、表面粗さRaが小さく、かつピットの発生が抑制された表面が効果的に実現され得る。化合物Cphoは、一種を単独でまたは二種以上を組み合わせて用いることができる。 (Compound Cpho )
The polishing composition disclosed here contains a compound Cpho having a phosphate group or a phosphonic acid group as an essential component. By including the compound Cpho in a polishing composition containing abrasive grains, it is possible to suppress the surface roughness of the polishing object due to polishing and improve the surface quality after polishing. Thereby, the surface where surface roughness Ra is small and generation | occurrence | production of the pit was suppressed can be implement | achieved effectively. Compound Cpho can be used alone or in combination of two or more.
リン酸または亜リン酸とエステル結合を形成する有機基としては、C1-20程度の炭化水素基が好ましく、C1-12の炭化水素基がより好ましく、C1-8の炭化水素基がさらに好ましく、C1-4の炭化水素基が特に好ましい。なお、この明細書において、CX-Yとは、「炭素原子数X以上Y以下」を意味する。上記炭化水素基は、脂肪族性でもよく、芳香族性でもよい。脂肪族性炭化水素基は、飽和でも不飽和でもよく、鎖状でも環状でもよく、直鎖状でも分岐状でもよい。
ここに開示される研磨用組成物のいくつかの態様において、化合物Cphoとして、リン酸モノC1-4アルキルエステルおよびリン酸ジC1-4アルキルエステルからなる群から選択される少なくとも一種を好ましく使用し得る。例えば、化合物Cphoとして、リン酸モノエチルとリン酸ジエチルとの混合物を用いることができる。 Examples of the compound Cpho , which is an organic compound, include phosphate esters and phosphites. As the phosphate esters, monoesters and diesters are preferably used, and a mixture of monoesters and diesters may be used. The molar ratio of monoester to diester in the above mixture may be, for example, 20:80 to 80:20, or 40:60 to 60:40. Moreover, as said phosphites, a monoester can be used preferably.
The organic group that forms an ester bond with phosphoric acid or phosphorous acid is preferably a hydrocarbon group of about C 1-20 , more preferably a C 1-12 hydrocarbon group, and a C 1-8 hydrocarbon group. More preferred is a C 1-4 hydrocarbon group. In this specification, C XY means “the number of carbon atoms is X or more and Y or less”. The hydrocarbon group may be aliphatic or aromatic. The aliphatic hydrocarbon group may be saturated or unsaturated, may be linear or cyclic, and may be linear or branched.
In some embodiments of the polishing composition disclosed herein, the compound C pho includes at least one selected from the group consisting of mono-C 1-4 alkyl esters of phosphoric acid and di-C 1-4 alkyl esters of phosphoric acid. It can be preferably used. For example, as the compound Cpho , a mixture of monoethyl phosphate and diethyl phosphate can be used.
有機化合物である化合物Cphoの他の例としては、リン酸または亜リン酸と有機カチオンとの塩等が挙げられる。 The compound Cpho , which is an organic compound, may be a chelate compound having a phosphonic acid group. Examples of such compounds C pho, 1-hydroxyethylidene-1,1-diphosphonic acid, amino tri (methylene phosphonic acid), ethylenediamine tetra (methylene phosphonic acid), diethylenetriamine penta (methylene phosphonic acid), ethane-1, 1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane-1,2- Chelate compounds having two or more phosphonic acid groups in one molecule, such as dicarboxy-1,2-diphosphonic acid; 2-aminoethylphosphonic acid, methanehydroxyphosphonic acid, 2-phosphonobutane-1,2-dicarboxylic acid 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid, etc. Chelate compounds with one phosphonic acid group in, and the like. From the viewpoint of favorably achieving both suppression of reduction in polishing efficiency and improvement in surface quality after polishing, the number of phosphonic acid groups possessed by the compound C pho is advantageously 1 or more and 4 or less per molecule. It is preferably 1 or more and 3 or less, particularly preferably 1 or 2. From the same viewpoint, the molecular weight of the compound Cpho is advantageously 800 or less, preferably 600 or less, more preferably 400 or less, and further preferably 300 or less or 250 or less.
Other examples of the compound Cpho , which is an organic compound, include a salt of phosphoric acid or phosphorous acid and an organic cation.
ここに開示される研磨用組成物は、本発明の効果を大きく損なわない限度で、必要に応じて酸化剤を含んでいてもよい。研磨用組成物が酸化剤を含む場合における該酸化剤の濃度は、例えば、0重量%を超えて5.0重量%以下とすることができる。
ここに開示される研磨用組成物のいくつかの態様において、該研磨用組成物は、酸化剤の濃度が所定以下であることが好ましく、酸化剤を含まなくてもよい。特に、研磨対象材料表面の仕上げ研磨工程に用いられる研磨用組成物では、酸化剤の濃度が所定以下であることが好ましい。 (Oxidant)
The polishing composition disclosed herein may contain an oxidizer as necessary, as long as the effects of the present invention are not significantly impaired. When the polishing composition contains an oxidizing agent, the concentration of the oxidizing agent can be, for example, more than 0% by weight and 5.0% by weight or less.
In some embodiments of the polishing composition disclosed herein, the polishing composition preferably has an oxidant concentration of a predetermined level or less, and may not contain an oxidant. In particular, in the polishing composition used in the finish polishing step on the surface of the material to be polished, the concentration of the oxidizing agent is preferably not more than a predetermined value.
ここに開示される研磨用組成物のpHは、5.0未満であることが好ましく、3.0未満であることが好ましい。より低いpHの研磨用組成物を使用することにより、研磨能率は向上する傾向にある。いくつかの態様において、研磨用組成物のpHは、例えば2.5以下であってよく、2.5未満でもよく、2.0未満でもよく、1.5未満でもよく、1.3未満でもよい。ここに開示される研磨用組成物によると、該組成物が化合物Cphoを含むことにより、低pHにおいても研磨対象物表面の荒れを効果的に抑制することができる。このことによって、良好な研磨能率と高い面品質とを好適に両立することができる。研磨用組成物のpHの下限は特に制限されないが、設備の腐蝕抑制や環境衛生の観点から、通常は0.5以上であることが適当であり、0.7以上であってもよい。
なお、この明細書において、pHは、pHメーターを使用し、標準緩衝液(フタル酸塩pH緩衝液 pH:4.01(25℃)、中性リン酸塩pH緩衝液 pH:6.86(25℃)、炭酸塩pH緩衝液 pH:10.01(25℃))を用いて3点校正した後で、ガラス電極を測定対象の組成物に入れて、2分以上経過して安定した後の値を測定することにより把握することができる。pHメーターとしては、例えば、堀場製作所製のガラス電極式水素イオン濃度指示計(型番F-23)またはその相当品を使用する。 (PH)
The polishing composition disclosed herein preferably has a pH of less than 5.0, preferably less than 3.0. By using a polishing composition having a lower pH, the polishing efficiency tends to be improved. In some embodiments, the polishing composition may have a pH of, for example, 2.5 or less, less than 2.5, less than 2.0, less than 1.5, or less than 1.3. Good. According to the polishing composition disclosed here, when the composition contains the compound Cpho , it is possible to effectively suppress the roughness of the surface of the polishing object even at a low pH. This makes it possible to achieve both good polishing efficiency and high surface quality. The lower limit of the pH of the polishing composition is not particularly limited, but it is usually suitably 0.5 or more and 0.7 or more from the viewpoint of inhibiting corrosion of equipment and environmental hygiene.
In this specification, pH is measured using a pH meter, standard buffer solution (phthalate pH buffer solution pH: 4.01 (25 ° C.), neutral phosphate pH buffer solution pH: 6.86 ( 25 ° C.), after calibrating three points using a carbonate pH buffer solution (pH: 10.01 (25 ° C.)), the glass electrode was put into the composition to be measured, and after 2 minutes had elapsed, the glass electrode was stabilized. Can be determined by measuring the value of. As the pH meter, for example, a glass electrode type hydrogen ion concentration indicator (model number F-23) manufactured by HORIBA, Ltd. or an equivalent thereof is used.
ここに開示される研磨用組成物は、必須成分である砥粒、水および化合物Cphoの他に、必要に応じてpH調整等の目的で用いられる任意成分として、一種または二種以上の酸を含んでいてもよい。化合物Cphoに該当する酸、すなわちリン酸、亜リン酸、ホスホン酸は、ここでいう酸の例には含まれない。酸の具体例としては、硫酸、硝酸、塩酸、ホスフィン酸、ホウ酸等の無機酸;酢酸、イタコン酸、コハク酸、酒石酸、クエン酸、マレイン酸、グリコール酸、マロン酸、メタンスルホン酸、ギ酸、リンゴ酸、グルコン酸、アラニン、グリシン、乳酸、トリフルオロ酢酸、トリフルオロメタンスルホン酸等の有機酸;等が挙げられる。酸は、該酸の塩の形態で用いられてもよい。上記酸の塩は、例えば、ナトリウム塩やカリウム塩等のアルカリ金属塩や、アンモニウム塩等であり得る。化合物Cphoと酸とを組み合わせて用いることにより、上記酸を用いない場合に比べて化合物Cphoの使用量を減らしても、良好な面品質を効率よく実現し得る。このことは経済性や環境負荷軽減の観点から有利となり得る。 (acid)
The polishing composition disclosed herein includes one or two or more acids as optional components used for the purpose of adjusting pH, etc., if necessary, in addition to the essential components of abrasive grains, water and compound Cpho. May be included. Acids corresponding to the compound Cpho , that is, phosphoric acid, phosphorous acid, and phosphonic acid are not included in the examples of acids mentioned here. Specific examples of acids include inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphinic acid, boric acid; acetic acid, itaconic acid, succinic acid, tartaric acid, citric acid, maleic acid, glycolic acid, malonic acid, methanesulfonic acid, formic acid And organic acids such as malic acid, gluconic acid, alanine, glycine, lactic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and the like. The acid may be used in the form of a salt of the acid. The acid salt may be, for example, an alkali metal salt such as a sodium salt or a potassium salt, or an ammonium salt. By using the compound C pho and an acid in combination, even when the amount of the compound C pho used is reduced as compared with the case where the acid is not used, good surface quality can be efficiently realized. This can be advantageous from the viewpoint of economy and reduction of environmental load.
m1/(m1+m2)≧0.1;
を満たすように設定することができる。すなわち、モル基準で、研磨用組成物1kg当たりに含まれる化合物Cphoと酸との合計量のうち10%以上が化合物Cphoであることが好ましい。このように設定することにより、研磨能率と研磨後の良好な面品質とがバランスよく両立する傾向にある。m1/(m1+m2)が0.15以上または0.20以上である研磨用組成物によると、より好適な結果が実現され得る。m1/(m1+m2)は、典型的には1未満であり、0.95未満または0.90未満でもよい。 When the polishing composition disclosed herein contains the compound C pho and an acid (preferably a strong acid) in combination, their contents are the compound m pho content m1 [mol / kg] and the acid content. The relationship with m2 [mol / kg] is as follows:
m1 / (m1 + m2) ≧ 0.1;
Can be set to satisfy. That is, on a molar basis, is preferably 10% or more of the total amount of the compound C pho and acid contained per polishing composition 1kg is a compound C pho. By setting in this way, the polishing efficiency and the good surface quality after polishing tend to be compatible with each other in a well-balanced manner. According to the polishing composition in which m1 / (m1 + m2) is 0.15 or more or 0.20 or more, a more preferable result can be realized. m1 / (m1 + m2) is typically less than 1 and may be less than 0.95 or less than 0.90.
このような上記(A)の化合物Cphoの含有量m1Aと酸の含有量m2との関係は、ここに開示される研磨用組成物が上記(B)に属する化合物Cphoと酸(好ましくは強酸)とを組み合わせて含む場合における上記(B)の化合物Cphoの含有量m1Bと酸の含有量m2との関係や、ここに開示される研磨用組成物が上記(D)に属する化合物Cphoと酸(好ましくは強酸)とを組み合わせて含む場合における上記(D)の化合物Cphoの含有量m1Dと酸の含有量m2との関係にも好ましく適用され得る。 When the polishing composition disclosed herein contains a combination of the compound C pho belonging to the above (A) and an acid (preferably a strong acid), the content m1A [mol / kg] of the compound C pho of the above (A) Can be set so that m1A / (m1A + m2) is 0.15 or more, for example. From the viewpoint of improving the surface quality after polishing, m1A / (m1A + m2) is preferably 0.20 or more. m1A / (m1A + m2) is typically less than 1, and may be less than 0.90 or less than 0.80, less than 0.70, or less than 0.60 from the viewpoint of improving polishing efficiency. In some embodiments, m1A / (m1A + m2) may be less than 0.50, less than 0.40, and less than 0.30.
Relationship between the content m2 content m1A and acid compound C pho of such (A) above, the compound C pho and acid polishing compositions disclosed herein belongs to the (B) (preferably In the case of containing a combination of (strong acid) and the compound C pho content m1B of the above (B) and the acid content m2, the polishing composition disclosed here is a compound C belonging to the above (D) pho and the acid (preferably a strong acid) may be preferably applied to a relationship between the content m2 content m1D and acid compound C pho (D) above in a case that includes a combination of a.
ここに開示される研磨用組成物は、本発明の効果を損なわない範囲で、キレート剤、増粘剤、分散剤、表面保護剤、濡れ剤、有機または無機の塩基、界面活性剤、防錆剤、防腐剤、防カビ剤等の、研磨用組成物(典型的には高硬度材料研磨用組成物、例えば窒化ガリウム基板研磨用組成物)に用いられ得る公知の添加剤を、必要に応じてさらに含有してもよい。 (Other ingredients)
The polishing composition disclosed herein is a chelating agent, a thickening agent, a dispersant, a surface protecting agent, a wetting agent, an organic or inorganic base, a surfactant, and a rust-proofing agent as long as the effects of the present invention are not impaired. Known additives that can be used in polishing compositions (typically high-hardness material polishing compositions such as gallium nitride substrate polishing compositions), such as agents, preservatives, and fungicides, as needed. It may be further contained.
ここに開示される研磨用組成物の製造方法は特に限定されない。例えば、翼式攪拌機、超音波分散機、ホモミキサー等の周知の混合装置を用いて、研磨用組成物に含まれる各成分を混合するとよい。これらの成分を混合する態様は特に限定されず、例えば全成分を一度に混合してもよく、適宜設定した順序で混合してもよい。 <Manufacture of polishing composition>
The manufacturing method of polishing composition disclosed here is not specifically limited. For example, each component contained in the polishing composition may be mixed using a well-known mixing device such as a blade-type stirrer, an ultrasonic disperser, or a homomixer. The aspect which mixes these components is not specifically limited, For example, all the components may be mixed at once and may be mixed in the order set suitably.
ここに開示される研磨用組成物は、例えば以下の操作を含む態様で、研磨対象物の研磨に使用することができる。
すなわち、ここに開示されるいずれかの研磨用組成物を含む研磨液を用意する。上記研磨液を用意することには、研磨用組成物を希釈することが含まれ得る。あるいは、上記研磨用組成物をそのまま研磨液として使用してもよい。また、多剤型の研磨用組成物の場合、上記研磨液を用意することには、それらの剤を混合すること、該混合の前に1または複数の剤を希釈すること、該混合の後にその混合物を希釈すること、等が含まれ得る。
次いで、その研磨液を研磨対象物表面に供給し、常法により研磨する。例えば、一般的な研磨装置に研磨対象物をセットし、該研磨装置の研磨パッドを通じて該研磨対象物の表面(研磨対象面)に上記研磨液を供給する。典型的には、上記研磨液を連続的に供給しつつ、研磨対象物の表面に研磨パッドを押しつけて両者を相対的に移動(例えば回転移動)させる。かかるポリシング工程を経て研磨対象物の研磨が完了する。 <Polishing method>
The polishing composition disclosed herein can be used for polishing a polishing object, for example, in an embodiment including the following operations.
That is, a polishing liquid containing any of the polishing compositions disclosed herein is prepared. Preparing the polishing liquid can include diluting the polishing composition. Or you may use the said polishing composition as polishing liquid as it is. Further, in the case of a multi-drug type polishing composition, to prepare the polishing liquid, mixing those agents, diluting one or more agents before the mixing, and after the mixing Diluting the mixture, etc. can be included.
Next, the polishing liquid is supplied to the surface of the object to be polished and polished by a conventional method. For example, a polishing object is set in a general polishing apparatus, and the polishing liquid is supplied to the surface (polishing object surface) of the polishing object through a polishing pad of the polishing apparatus. Typically, while supplying the polishing liquid continuously, the polishing pad is pressed against the surface of the object to be polished, and both are relatively moved (for example, rotated). The polishing of the object to be polished is completed through the polishing step.
ここに開示される研磨用組成物を仕上げ研磨工程において使用する場合、該仕上げ研磨工程に先立って行われる予備研磨工程は、典型的には、砥粒および水を含む予備研磨工程用組成物を用いて行われる。以下、予備研磨工程用組成物に含まれる砥粒のことを、予備研磨用砥粒ということがある。 (Preliminary polishing composition)
When the polishing composition disclosed herein is used in a final polishing step, the preliminary polishing step performed prior to the final polishing step typically includes a preliminary polishing step composition containing abrasive grains and water. Is done using. Hereinafter, the abrasive grains contained in the preliminary polishing step composition may be referred to as preliminary polishing abrasive grains.
予備研磨用組成物に使用する酸化剤の具体例としては、過酸化水素;硝酸化合物類、例えば硝酸鉄、硝酸銀、硝酸アルミニウム等の硝酸塩や、硝酸セリウムアンモニウム等の硝酸錯体;過硫酸化合物類、例えば過硫酸ナトリウム、過硫酸カリウム等の過硫酸金属塩や過硫酸アンモニウムのような過硫酸塩;塩素酸化合物類または過塩素酸化合物類、例えば過塩素酸カリウム等の過塩素酸塩や塩素酸塩;臭素酸化合物、例えば臭素酸カリウム等の臭素酸塩;ヨウ素酸化合物類、例えばヨウ素酸アンモニウム等のヨウ素酸塩;過ヨウ素酸化合物類、例えば過ヨウ素酸ナトリウム等の過ヨウ素酸塩;ジクロロイソシアヌル酸ナトリウム、ジクロロイソシアヌル酸カリウム等のジクロロイソシアヌル酸塩;鉄酸化合物類、例えば鉄酸カリウム等の鉄酸塩;過マンガン酸化合物類、例えば過マンガン酸ナトリウム、過マンガン酸カリウム等の過マンガン酸塩;クロム酸化合物類、例えばクロム酸カリウム、二クロム酸カリウム等のクロム酸塩;バナジン酸化合物類、例えばメタバナジン酸アンモニウム、メタバナジン酸ナトリウム、メタバナジン酸カリウム等のメタバナジン酸塩;過ルテニウム酸塩等の過ルテニウム酸化合物類;モリブデン酸化合物類、例えばモリブデン酸アンモニウム、モリブデン酸二ナトリウム等のモリブデン酸塩;過レニウム酸塩等の過レニウム酸化合物類;タングステン酸化合物類、例えばタングステン酸二ナトリウム等のタングステン酸塩;が挙げられる。これらは1種を単独でまたは2種以上を適宜組み合わせて用いることができる。 The preliminary polishing composition can contain one or more oxidizing agents as optional components. The oxidizing agent can be useful for improving the polishing efficiency and reducing the surface roughness in the preliminary polishing step.
Specific examples of the oxidizing agent used in the preliminary polishing composition include hydrogen peroxide; nitrate compounds, for example, nitrates such as iron nitrate, silver nitrate, and aluminum nitrate; nitrate complexes such as cerium ammonium nitrate; For example, persulfate metal salts such as sodium persulfate and potassium persulfate and persulfates such as ammonium persulfate; chlorate compounds or perchlorate compounds such as perchlorate and chlorate such as potassium perchlorate Bromate compounds such as bromate salts such as potassium bromate; iodate compounds such as iodate such as ammonium iodate; periodate compounds such as periodate such as sodium periodate; dichloroisocyanuric Dichloroisocyanurates such as sodium acid and potassium dichloroisocyanurate; iron acid compounds such as iron acids such as potassium ferrate Permanganate compounds such as permanganate such as sodium permanganate and potassium permanganate; chromate compounds such as chromate such as potassium chromate and potassium dichromate; vanadic acid compounds such as Metavanadates such as ammonium metavanadate, sodium metavanadate and potassium metavanadate; perruthenic acid compounds such as perruthenate; molybdates such as molybdate such as ammonium molybdate and disodium molybdate; Perrhenic acid compounds such as rhenic acid salts; tungstic acid compounds such as tungstates such as disodium tungstate. These can be used singly or in appropriate combination of two or more.
予備研磨用組成物のpHが5.0未満である場合、該予備研磨用組成物は、酸化剤を含有してもよく、酸化剤を含有しなくてもよい。例えば、pHが2.0未満であって、少なくとも過酸化水素を含有しない予備研磨用組成物を好ましく用いることができる。pH5.0未満の予備研磨用組成物に酸化剤を含有させる場合、該酸化剤としては、例えば過硫酸金属塩を用いることができる。予備研磨用組成物は、pH5.0未満またはpH3.0未満であって、過硫酸金属塩を含有し、かつ過酸化水素を含有しない組成であり得る。 In some embodiments, the pre-polishing composition can be acidic with a pH of less than 7.0. The pH of the preliminary polishing composition may be less than 5.0, less than 3.0, or less than 2.5. In particular, the pH of the preliminary polishing composition is preferably less than 2.0, less than 1.5 or less than 1.2. The polishing efficiency tends to be improved by using a lower pH pre-polishing composition. After polishing with such a strongly acidic pre-polishing composition, by performing final polishing using the polishing composition disclosed herein, a high-quality surface can be efficiently obtained.
When the pH of the preliminary polishing composition is less than 5.0, the preliminary polishing composition may contain an oxidizing agent or may not contain an oxidizing agent. For example, a preliminary polishing composition having a pH of less than 2.0 and containing at least hydrogen peroxide can be preferably used. When the pre-polishing composition having a pH of less than 5.0 contains an oxidizing agent, for example, a persulfate metal salt can be used as the oxidizing agent. The pre-polishing composition may be a composition having a pH of less than 5.0 or less than 3.0 and containing a metal persulfate and no hydrogen peroxide.
予備研磨用組成物のpHが5.0以上である場合、該予備研磨用組成物は、酸を含有してもよく、含有しなくてもよい。例えば、pHが5.5以上であって、少なくとも強酸を含有しない予備研磨用組成物を好ましく用いることができる。 In some embodiments, the pH of the preliminary polishing composition may be, for example, 5.0 or more, 5.5 or more, or 6.0 or more. Further, the pH of the preliminary polishing composition may be, for example, 10 or less, or 8.0 or less. Thus, the preliminary polishing composition having a weakly acidic to weakly alkaline liquid property has an advantage of good handleability. The preliminary polishing composition having liquid properties preferably contains an oxidizing agent. After polishing with a pre-polishing composition having a weak acidity to weak alkalinity and containing an oxidizer, by performing final polishing using the polishing composition disclosed herein, a high-quality surface is efficiently obtained. Obtainable.
When the pH of the preliminary polishing composition is 5.0 or more, the preliminary polishing composition may or may not contain an acid. For example, a preliminary polishing composition having a pH of 5.5 or higher and containing at least no strong acid can be preferably used.
ここで、硬度の高いものとはAskerC硬度が80より高い研磨パッドであり、硬度の低いものとはAskerC硬度が80以下の研磨パッドである。硬度の高い研磨パッドとは、例えば硬質発泡ポリウレタンタイプや不織布タイプの研磨パッドである。硬度の低い研磨パッドとは、好適には、少なくとも研磨対象物に押しつけられる側が軟質発泡ポリウレタン等の軟質発泡樹脂により構成されている研磨パッドであり、例えばスウェードタイプの研磨パッドである。スウェードタイプの研磨パッドは、典型的には、研磨対象物に押しつけられる側が軟質発泡ポリウレタンにより構成されている。AskerC硬度は、Asker社製のアスカーゴム硬度計C型を用いて測定することができる。ここに開示される研磨用組成物による研磨は、例えば、スウェードタイプの研磨パッドを用いて好ましく実施され得る。特に、仕上げ研磨工程ではスウェードタイプの研磨パッドを用いることが好ましい。 The polishing pad used for polishing in each of the preliminary polishing step and the final polishing step is not particularly limited. For example, any one having high hardness, low hardness, including abrasive grains, or not including abrasive grains may be used. It is preferable to use a polishing pad that does not contain abrasive grains at least in the second polishing step. For example, it is preferable to use a polishing pad that does not contain abrasive grains in both the first and second polishing steps.
Here, a high hardness is a polishing pad having an Asker C hardness higher than 80, and a low hardness is a polishing pad having an Asker C hardness of 80 or less. The polishing pad with high hardness is, for example, a hard foam polyurethane type or a nonwoven fabric type polishing pad. The polishing pad with low hardness is preferably a polishing pad in which at least the side pressed against the object to be polished is made of a soft foamed resin such as soft foamed polyurethane, for example, a suede type polishing pad. The suede type polishing pad is typically made of soft foamed polyurethane on the side pressed against the object to be polished. Asker C hardness can be measured using Asker rubber hardness meter C type manufactured by Asker. Polishing with the polishing composition disclosed herein can be preferably performed using, for example, a suede type polishing pad. In particular, it is preferable to use a suede type polishing pad in the final polishing step.
ここに開示される技術には、上記研磨用組成物を用いた研磨工程を含む研磨物の製造方法(例えば、窒化ガリウム基板または酸化ガリウム素基板の製造方法)および該方法により製造された研磨物の提供が含まれ得る。すなわち、ここに開示される技術によると、研磨対象材料から構成された研磨対象物に、ここに開示されるいずれかの研磨用組成物を供給して該研磨対象物を研磨することを含む、研磨物の製造方法および該方法により製造された研磨物が提供される。上記製造方法は、ここに開示されるいずれかの研磨方法の内容を好ましく適用することにより実施され得る。上記製造方法によると、高品質な表面を有する研磨物(例えば、窒化ガリウム基板、酸化ガリウム素基板等)が効率的に提供され得る。 <Manufacturing method of polished article>
The technique disclosed herein includes a method for producing a polished article (for example, a method for producing a gallium nitride substrate or a gallium oxide substrate) including a polishing step using the polishing composition, and a polished article produced by the method. Offerings may be included. That is, according to the technique disclosed herein, the method includes supplying a polishing composition disclosed herein to a polishing object composed of a material to be polished and polishing the polishing object. A method for producing an abrasive and an abrasive produced by the method are provided. The above manufacturing method can be implemented by preferably applying the contents of any of the polishing methods disclosed herein. According to the above manufacturing method, a polished product (for example, a gallium nitride substrate, a gallium oxide substrate, etc.) having a high-quality surface can be efficiently provided.
ここに開示される研磨方法は、典型的には、ガリウム化合物系半導体基板(以下、単に「基板」ともいう。)のポリシング工程に適用される。上記基板には、上記第一研磨工程の前に、研削(グラインディング)やラッピング等の、ポリシング工程より上流の工程においてガリウム化合物系半導体基板に適用され得る一般的な処理が施されていてもよい。 <Polishing method>
The polishing method disclosed herein is typically applied to a polishing process for a gallium compound semiconductor substrate (hereinafter also simply referred to as “substrate”). Before the first polishing step, the substrate may be subjected to a general process that can be applied to the gallium compound semiconductor substrate in a process upstream of the polishing process, such as grinding (grinding) or lapping. Good.
ここに開示される技術におけるスラリーS2は、砥粒A2と、水と、化合物Cphoとを含む。スラリーS2としては、上述した研磨用組成物と同様のものを好ましく使用し得る。 <Slurry S2>
The slurry S2 in the technique disclosed herein includes abrasive grains A2, water, and a compound Cpho . As slurry S2, the thing similar to the polishing composition mentioned above can be used preferably.
ここに開示される技術におけるスラリーS2は、砥粒A2を含む。砥粒A2としては、上述した研磨用組成物に含まれる砥粒と同様のものを好ましく使用し得る。スラリーS2における砥粒A2の濃度は、特に限定されないが、上述した研磨用組成物における砥粒の濃度と同様の濃度とすることができる。 (Abrasive grain A2)
The slurry S2 in the technology disclosed herein includes abrasive grains A2. As abrasive grain A2, the thing similar to the abrasive grain contained in the polishing composition mentioned above can be used preferably. Although the density | concentration of the abrasive grain A2 in slurry S2 is not specifically limited, It can be set as the density | concentration similar to the density | concentration of the abrasive grain in the polishing composition mentioned above.
スラリーS2は、必須成分として水を含む。スラリーS2に含まれる水としては、上述した研磨用組成物に含まれる水と同様のものを好ましく使用し得る。 (water)
The slurry S2 contains water as an essential component. As the water contained in the slurry S2, the same water as that contained in the above-described polishing composition can be preferably used.
ここに開示される技術におけるスラリーS2は、リン酸基またはホスホン酸基を有する化合物Cphoを、必須成分として含有する。砥粒A2を含むスラリーS2に化合物Cphoを含有させることにより、該スラリーS2を用いる研磨において、研磨対象物表面の荒れを抑制し、研磨後の面品質を改善することができる。これにより、表面粗さRaの小さい表面が効果的に実現され得る。また、化合物Cphoは、研磨対象物表面におけるピットの発生抑制にも役立ち得る。化合物Cphoは、一種を単独でまたは二種以上を組み合わせて用いることができる。スラリーS2に含まれる化合物Cphoとしては、上述した研磨用組成物に含まれる化合物Cphoと同様のものを好ましく使用し得る。スラリーS2における化合物Cphoの濃度[重量%]は特に限定されないが、上述した研磨用組成物における化合物Cphoの濃度と同様の濃度とすることができる。 (Compound Cpho )
The slurry S2 in the technique disclosed herein contains a compound Cpho having a phosphate group or a phosphonic acid group as an essential component. By including the compound Cpho in the slurry S2 containing the abrasive grains A2, it is possible to suppress the roughness of the surface of the object to be polished and improve the surface quality after polishing in the polishing using the slurry S2. Thereby, a surface with small surface roughness Ra can be effectively realized. Further, the compound Cpho can be useful for suppressing the generation of pits on the surface of the polishing object. Compound Cpho can be used alone or in combination of two or more. As the compound C pho contained in the slurry S2, it may be preferably used those similar to compounds C pho contained in the polishing composition as defined above. The concentration [wt%] of the compound C pho in the slurry S2 is not particularly limited, but may be the same concentration as the concentration of the compound C pho in the polishing composition described above.
ここに開示される技術におけるスラリーS2は、化合物Cphoによる面品質の向上効果をよりよく発揮させる観点から、酸化剤を含有しないか、または酸化剤の濃度が所定以下であることが好ましい。スラリーS2における酸化剤の濃度は、0.1重量%未満であることが好ましく、より好ましくは0.05重量%未満、さらに好ましくは0.02重量%未満、特に好ましくは0.01重量%未満である。スラリーS2が酸化剤を含有する場合、該酸化剤は、後述するスラリーS1に用いられ得る酸化剤と同様のものから選択することができる。スラリーS1,S2がいずれも酸化剤を含有する態様において、スラリーS1に含まれる酸化剤と、スラリーS2に含まれる酸化剤とは、同一であってもよく、異なっていてもよい。 (Oxidant)
The slurry S2 in the technique disclosed herein preferably does not contain an oxidant or the concentration of the oxidant is not more than a predetermined value from the viewpoint of better exhibiting the surface quality improvement effect by the compound Cpho . The concentration of the oxidizing agent in the slurry S2 is preferably less than 0.1% by weight, more preferably less than 0.05% by weight, still more preferably less than 0.02% by weight, particularly preferably less than 0.01% by weight. It is. When the slurry S2 contains an oxidizing agent, the oxidizing agent can be selected from the same oxidizing agents that can be used for the slurry S1 described later. In an embodiment in which both of the slurries S1 and S2 contain an oxidizing agent, the oxidizing agent contained in the slurry S1 and the oxidizing agent contained in the slurry S2 may be the same or different.
スラリーS2のpHは、上述した研磨用組成物のpHと同程度の範囲とすることができる。 (PH)
The pH of the slurry S2 can be in the same range as the pH of the polishing composition described above.
スラリーS2は、必須成分である砥粒、水および化合物Cphoの他に、必要に応じてpH調整等の目的で用いられる任意成分として、一種または二種以上の酸を含んでいてもよい。化合物Cphoに該当する酸、すなわちリン酸、亜リン酸、ホスホン酸は、ここでいう酸の例には含まれない。スラリーS2に含まれ得る酸としては、上述した研磨用組成物に含まれ得る酸と同様のものを好ましく使用し得る。酸の濃度は特に限定されないが、上述した研磨用組成物に含まれ得る酸と同様の濃度とすることができる。 (acid)
The slurry S2 may contain one or two or more acids as optional components used for the purpose of adjusting pH, etc., if necessary, in addition to the essential components of abrasive grains, water, and compound Cpho . Acids corresponding to the compound Cpho , that is, phosphoric acid, phosphorous acid, and phosphonic acid are not included in the examples of acids mentioned here. As the acid that can be contained in the slurry S2, the same acid that can be contained in the polishing composition described above can be preferably used. The concentration of the acid is not particularly limited, but may be the same concentration as the acid that can be contained in the polishing composition described above.
スラリーS2は、本発明の効果を損なわない範囲で、キレート剤、増粘剤、分散剤、表面保護剤、濡れ剤、有機または無機の塩基、界面活性剤、防錆剤、防腐剤、防カビ剤等の、研磨用組成物(典型的には高硬度材料研磨用組成物、例えば窒化ガリウム基板研磨用組成物)に用いられ得る公知の添加剤を、必要に応じてさらに含有してもよい。 (Other ingredients)
Slurry S2 is a chelating agent, thickener, dispersant, surface protective agent, wetting agent, organic or inorganic base, surfactant, rust preventive, antiseptic, antifungal, as long as the effects of the present invention are not impaired. A known additive that can be used for a polishing composition (typically a composition for polishing a high-hardness material, such as a composition for polishing a gallium nitride substrate), such as an agent, may be further contained as necessary. .
スラリーS2の製造方法は、特に限定されない。例えば、翼式攪拌機、超音波分散機、ホモミキサー等の周知の混合装置を用いて、スラリーS2に含まれる各成分を混合するとよい。これらの成分を混合する態様は特に限定されず、例えば全成分を一度に混合してもよく、適宜設定した順序で混合してもよい。スラリーS1についても同様である。 (Manufacturing method of slurry S2)
The method for producing the slurry S2 is not particularly limited. For example, each component contained in the slurry S2 may be mixed using a well-known mixing device such as a blade-type stirrer, an ultrasonic disperser, or a homomixer. The aspect which mixes these components is not specifically limited, For example, all the components may be mixed at once and may be mixed in the order set suitably. The same applies to the slurry S1.
第一研磨工程に用いられるスラリーS1は、砥粒A1と水とを含む。スラリーS1としては、上述した予備研磨用組成物と同様のものを好ましく使用し得る。水としては、スラリーS2と同様のものを好ましく使用し得る。 <Slurry S1>
The slurry S1 used in the first polishing step includes abrasive grains A1 and water. As slurry S1, the thing similar to the composition for preliminary polishing mentioned above can be used preferably. As the water, the same water as in the slurry S2 can be preferably used.
砥粒A1の材質や性状は、特に制限されない。砥粒A1として使用し得る材料としては、例えば、シリカ粒子、アルミナ、酸化セリウム、酸化クロム、二酸化チタン、酸化ジルコニウム、酸化マグネシウム、二酸化マンガン、酸化亜鉛、酸化鉄等の酸化物;窒化ケイ素、窒化ホウ素等の窒化物;炭化ケイ素、炭化ホウ素等の炭化物;ダイヤモンド;炭酸カルシウムや炭酸バリウム等の炭酸塩;等のいずれかから実質的に構成される砥粒が挙げられる。なかでも、シリカ、アルミナ、酸化セリウム、酸化クロム、酸化ジルコニウム、二酸化マンガン、酸化鉄等の酸化物から実質的に構成される砥粒は、良好な表面を形成し得るので好ましい。高い研磨能率と第二研磨工程後における高い面品質とを両立しやすくする観点から、シリカ砥粒、アルミナ砥粒、酸化ジルコニウム砥粒がより好ましく、シリカ砥粒、アルミナ砥粒が特に好ましい。 (Abrasive Grain A1)
The material and properties of the abrasive grain A1 are not particularly limited. Examples of materials that can be used as the abrasive grain A1 include silica particles, alumina, cerium oxide, chromium oxide, titanium dioxide, zirconium oxide, magnesium oxide, manganese dioxide, zinc oxide, iron oxide, and the like; silicon nitride, nitriding Abrasive grains substantially composed of any one of nitrides such as boron; carbides such as silicon carbide and boron carbide; diamonds; carbonates such as calcium carbonate and barium carbonate; Among these, abrasive grains substantially composed of oxides such as silica, alumina, cerium oxide, chromium oxide, zirconium oxide, manganese dioxide, and iron oxide are preferable because they can form a good surface. From the viewpoint of easily achieving both high polishing efficiency and high surface quality after the second polishing step, silica abrasive grains, alumina abrasive grains, and zirconium oxide abrasive grains are more preferable, and silica abrasive grains and alumina abrasive grains are particularly preferable.
いくつかの態様において、砥粒A1の平均二次粒子径は、好ましくは100nm以上であり、より好ましくは200nm以上であり、300nm以上または400nm以上であってもよい。このような平均二次粒子径を有する砥粒A1(例えばアルミナ砥粒)によると、第一研磨工程において高い研磨能率が得られやすい。
また、いくつかの態様において、砥粒A1の平均二次粒子径は、好ましくは300nm以下であり、より好ましくは200nm以下であり、150nm以下、100nm以下または80nm以下でもよい。このような平均二次粒子径を有する砥粒A1(例えばシリカ砥粒)によると、より短時間の第二研磨工程によっても高品質の表面を実現し得る。 The average secondary particle diameter of the abrasive grains A1 contained in the slurry S1 is usually 20 nm or more, and preferably 35 nm or more, more preferably 50 nm or more, and 60 nm or more from the viewpoint of polishing efficiency. Further, from the viewpoint of easily improving the surface quality in the second polishing step, the average secondary particle diameter of the abrasive grains A1 is usually appropriately 2000 nm or less, preferably 1000 nm or less, 800 nm or less, or 600 nm or less. .
In some embodiments, the average secondary particle diameter of the abrasive grains A1 is preferably 100 nm or more, more preferably 200 nm or more, and may be 300 nm or more or 400 nm or more. According to the abrasive grains A1 (for example, alumina abrasive grains) having such an average secondary particle diameter, high polishing efficiency is easily obtained in the first polishing step.
In some embodiments, the average secondary particle diameter of the abrasive grains A1 is preferably 300 nm or less, more preferably 200 nm or less, and may be 150 nm or less, 100 nm or less, or 80 nm or less. According to the abrasive grains A1 (for example, silica abrasive grains) having such an average secondary particle diameter, a high-quality surface can be realized even in a shorter second polishing step.
スラリーS1は、任意成分として、一種または二種以上の酸を含み得る。酸の使用により、スラリーS1のpHを調節することができる。例えば、酸を用いてスラリーS1のpHを2.0未満、1.5未満または1.0未満とすることにより、高い研磨効率が得られやすくなる。
スラリーS1に使用する酸は、上述した研磨用組成物(またはスラリーS2)に使用し得る酸として上記で例示した材料から適宜選択することができる。酸の濃度は、上述した研磨用組成物(またはスラリーS2)における酸の濃度と同程度の範囲から適宜選択することができる。 (acid)
The slurry S1 can contain one or more acids as optional components. The pH of the slurry S1 can be adjusted by using an acid. For example, when the pH of the slurry S1 is less than 2.0, less than 1.5, or less than 1.0 using an acid, high polishing efficiency is easily obtained.
The acid used for the slurry S1 can be appropriately selected from the materials exemplified above as the acid that can be used for the polishing composition (or the slurry S2). The acid concentration can be appropriately selected from a range similar to the acid concentration in the polishing composition (or slurry S2) described above.
スラリーS1は、任意成分として、一種または二種以上の酸化剤を含み得る。スラリーS1に酸化剤を含有させることにより、該スラリーS1を研磨対象物の表面に効果的に作用させることができる。したがって、スラリーS1に酸化剤を含有させることは、研磨効率向上や表面粗さ低減に役立ち得る。
スラリーS1に使用する酸化剤の具体例としては、過酸化水素;硝酸化合物類、例えば硝酸鉄、硝酸銀、硝酸アルミニウム等の硝酸塩や、硝酸セリウムアンモニウム等の硝酸錯体;過硫酸化合物類、例えば過硫酸ナトリウム、過硫酸カリウム等の過硫酸金属塩や過硫酸アンモニウムのような過硫酸塩;塩素酸化合物類または過塩素酸化合物類、例えば過塩素酸カリウム等の過塩素酸塩や塩素酸塩;臭素酸化合物、例えば臭素酸カリウム等の臭素酸塩;ヨウ素酸化合物類、例えばヨウ素酸アンモニウム等のヨウ素酸塩;過ヨウ素酸化合物類、例えば過ヨウ素酸ナトリウム等の過ヨウ素酸塩;ジクロロイソシアヌル酸ナトリウム、ジクロロイソシアヌル酸カリウム等のジクロロイソシアヌル酸塩;鉄酸化合物類、例えば鉄酸カリウム等の鉄酸塩;過マンガン酸化合物類、例えば過マンガン酸ナトリウム、過マンガン酸カリウム等の過マンガン酸塩;クロム酸化合物類、例えばクロム酸カリウム、二クロム酸カリウム等のクロム酸塩;バナジン酸化合物類、例えばメタバナジン酸アンモニウム、メタバナジン酸ナトリウム、メタバナジン酸カリウム等のメタバナジン酸塩;過ルテニウム酸塩等の過ルテニウム酸化合物類;モリブデン酸化合物類、例えばモリブデン酸アンモニウム、モリブデン酸二ナトリウム等のモリブデン酸塩;過レニウム酸塩等の過レニウム酸化合物類;タングステン酸化合物類、例えばタングステン酸二ナトリウム等のタングステン酸塩;が挙げられる。これらは1種を単独でまたは2種以上を適宜組み合わせて用いることができる。 (Oxidant)
The slurry S1 may contain one or more oxidizing agents as optional components. By containing an oxidizing agent in the slurry S1, the slurry S1 can effectively act on the surface of the object to be polished. Therefore, inclusion of an oxidizing agent in the slurry S1 can be useful for improving polishing efficiency and reducing surface roughness.
Specific examples of the oxidizing agent used in the slurry S1 include hydrogen peroxide; nitrate compounds such as nitrates such as iron nitrate, silver nitrate, and aluminum nitrate; nitrate complexes such as cerium ammonium nitrate; persulfate compounds such as persulfuric acid. Persulfate metal salts such as sodium and potassium persulfate and persulfates such as ammonium persulfate; Perchlorates and chlorates such as chlorate compounds or perchlorate compounds such as potassium perchlorate; Bromate Compounds, eg bromates such as potassium bromate; iodate compounds, eg iodates such as ammonium iodate; periodate compounds, eg periodate such as sodium periodate; sodium dichloroisocyanurate, Dichloroisocyanurate such as potassium dichloroisocyanurate; iron acid compounds, for example, iron salts such as potassium ferrate; Manganic acid compounds such as permanganate such as sodium permanganate and potassium permanganate; Chromate compounds such as chromate such as potassium chromate and potassium dichromate; Vanadate compounds such as metavanadate Metavanadates such as ammonium, sodium metavanadate and potassium metavanadate; perruthenic acid compounds such as perruthenate; molybdate compounds such as molybdate such as ammonium molybdate and disodium molybdate; perrhenic acid Perrhenic acid compounds such as salts; tungstic acid compounds such as tungstates such as disodium tungstate. These can be used singly or in appropriate combination of two or more.
スラリーS1のpHは特に限定されず、例えば、0.5~12程度の範囲から選択することができる。スラリーS1のpHは、該スラリーS1に含まれる他の成分の組成等を考慮して選択することができる。 (PH)
The pH of the slurry S1 is not particularly limited, and can be selected from a range of about 0.5 to 12, for example. The pH of the slurry S1 can be selected in consideration of the composition of other components contained in the slurry S1.
スラリーS1のpHが5.0未満である態様において、該スラリーS1は、酸化剤を含有してもよく、酸化剤を含有しなくてもよい。例えば、pHが2.0未満であって、少なくとも過酸化水素を含有しないスラリーS1を好ましく用いることができる。pH5.0未満のスラリーS1に酸化剤を含有させる場合、該酸化剤としては、例えば過硫酸金属塩を用いることができる。スラリーS1は、pH5.0未満またはpH3.0未満であって、過硫酸金属塩を含有し、かつ過酸化水素を含有しない組成であり得る。 In some embodiments, the slurry S1 can be acidic with a pH of less than 7.0. The pH of the slurry S1 may be less than 5.0, less than 3.0, or less than 2.5. In particular, the pH of the slurry S1 is preferably less than 2.0, less than 1.5 or less than 1.2. By using the slurry S1 having a lower pH, the polishing efficiency tends to be improved. In the polishing method disclosed herein, the polishing with the slurry S2 is further performed after the polishing with the slurry S1, and therefore the surface quality can be effectively improved in the second polishing step even when the strongly acidic slurry S1 is used. . Therefore, a high-quality surface can be efficiently obtained by performing in this order the first polishing step for polishing with the strongly acidic slurry S1 and the second polishing step for polishing with the slurry S2.
In the embodiment in which the pH of the slurry S1 is less than 5.0, the slurry S1 may contain an oxidizing agent or may not contain an oxidizing agent. For example, a slurry S1 having a pH of less than 2.0 and containing at least hydrogen peroxide can be preferably used. When the slurry S1 having a pH of less than 5.0 contains an oxidizing agent, for example, a persulfate metal salt can be used as the oxidizing agent. The slurry S1 may have a composition that is less than pH 5.0 or less than pH 3.0, contains a metal persulfate, and does not contain hydrogen peroxide.
スラリーS1のpHが5.0以上である態様において、該スラリーS1は、酸を含有してもよく、含有しなくてもよい。例えば、pHが5.5以上であって、少なくとも強酸を含有しないスラリーS1を好ましく用いることができる。 In some embodiments, the pH of the slurry S1 may be, for example, 5.0 or more, 5.5 or more, or 6.0 or more. Further, the pH of the slurry S1 may be 10 or less, for example, or 8.0 or less. Thus, the slurry S1 having a weakly acidic to weakly alkaline liquid property has an advantage that it is easy to handle. The liquid S1 preferably contains an oxidizing agent. By performing the first polishing step using the slurry S1 having a composition that is weakly acidic to weakly alkaline and contains an oxidizing agent, a surface suitable for improving the surface quality in the second polishing step can be efficiently realized.
In the embodiment in which the pH of the slurry S1 is 5.0 or more, the slurry S1 may or may not contain an acid. For example, a slurry S1 having a pH of 5.5 or higher and containing at least no strong acid can be preferably used.
スラリーS1には、任意成分として、リン酸基またはホスホン酸基を有する化合物Cphoを含有させることができる。スラリーS1に化合物Cphoを含有させることにより、第一研磨工程における表面の荒れを抑制する効果が発揮され得る。スラリーS1が化合物Cphoを含有する場合、該化合物Cphoは、スラリーS2に用いられ得る化合物Cphoと同様のものから選択することができる。スラリーS1,S2がいずれも化合物Cphoを含有する態様において、スラリーS1に含まれる化合物Cphoと、スラリーS2に含まれる化合物Cphoとは、同一であってもよく、異なっていてもよい。 (Compound Cpho )
The slurry S1 can contain a compound Cpho having a phosphoric acid group or a phosphonic acid group as an optional component. By containing the compound Cpho in the slurry S1, the effect of suppressing surface roughness in the first polishing step can be exhibited. If the slurry S1 contains a compound C pho, the compound C pho may be selected from those similar to the compound C pho that may be used in the slurry S2. In embodiments the slurry S1, S2 is containing a compound C pho both, the compound C pho contained in the slurry S1, and the compound C pho contained in the slurry S2, may be the same or may be different.
なお、上記合計研磨時間とは、第一研磨工程での研磨時間と第二研磨工程での研磨時間との合計を意味する。したがって、例えば第一研磨工程の研磨終了から第二研磨工程の研磨開始までの時間は、上記合計研磨時間には含まれない。 If the slurry S1 contains a compound C pho, concentration [wt%] of Compound C pho in the slurry S1 is, it is preferable to lower than the concentration of the compound C pho in the slurry S2 w1 [wt%]. Hereinafter, the concentration [wt%] of the compound Cpho in the slurry S1 may be expressed as wp. If wp is greater than or equal to w1, the efficiency of the entire multistage polishing process including the first and second polishing steps tends to decrease, and the total polishing time required to obtain a high-quality surface tends to increase. From these viewpoints, the concentration wp [wt%] of the compound C pho in case of incorporating the compound C pho the slurry S1 is against the concentration of compound C pho in the slurry S2 w1 [wt%], the 3/4 2/3 or less, 1/2 or less, 1/5 or less, or 1/10 or less.
The total polishing time means the total of the polishing time in the first polishing step and the polishing time in the second polishing step. Therefore, for example, the time from the end of polishing in the first polishing step to the start of polishing in the second polishing step is not included in the total polishing time.
スラリーS1は、本発明の効果を損なわない範囲で、キレート剤、増粘剤、分散剤、表面保護剤、濡れ剤、有機または無機の塩基、界面活性剤、防錆剤、防腐剤、防カビ剤等の、研磨用組成物(典型的には高硬度材料研磨用組成物、例えば窒化ガリウム基板研磨用組成物)に用いられ得る公知の添加剤を、必要に応じてさらに含有してもよい。 (Other ingredients)
Slurry S1 is a chelating agent, thickener, dispersant, surface protective agent, wetting agent, organic or inorganic base, surfactant, rust preventive, antiseptic, antifungal as long as the effects of the present invention are not impaired. A known additive that can be used for a polishing composition (typically a composition for polishing a high-hardness material, such as a composition for polishing a gallium nitride substrate), such as an agent, may be further contained as necessary. .
ここに開示される技術には、例えば、以下のような研磨用組成物セットの提供が含まれ得る。すなわち、ここに開示される技術によると、互いに分けて保管される組成物Q1および組成物Q2を含む研磨用組成物セットが提供される。上記組成物Q1は、ここに開示される研磨方法における第一研磨工程に用いられるスラリーS1またはその濃縮液であり得る。上記組成物Q2は、ここに開示される研磨方法における第二研磨工程に用いられるスラリーS2またはその濃縮液であり得る。このような構成の研磨用組成物セットによると、第一、第二研磨工程を含む多段研磨プロセスにおいて、高い研磨能率と、研磨後における高品質の表面とを好適に両立し得る。 <Polishing composition set>
The technology disclosed herein can include, for example, providing the following polishing composition set. That is, according to the technique disclosed herein, a polishing composition set including the composition Q1 and the composition Q2 stored separately from each other is provided. The composition Q1 may be the slurry S1 used in the first polishing step in the polishing method disclosed herein or a concentrated solution thereof. The composition Q2 may be the slurry S2 used in the second polishing step in the polishing method disclosed herein or a concentrated solution thereof. According to the polishing composition set having such a configuration, in a multistage polishing process including the first and second polishing steps, high polishing efficiency and a high-quality surface after polishing can be suitably achieved.
ここに開示される研磨方法は、第一研磨工程と第二研磨工程とをこの順に含む。第一研磨工程は、スラリーS1を含む研磨液を用いて研磨対象物を研磨する工程である。第二研磨工程は、第一研磨工程が行われた研磨対象物を、スラリーS2を含む研磨液を用いてさらに研磨する工程である。 <Polishing method>
The polishing method disclosed herein includes a first polishing step and a second polishing step in this order. A 1st grinding | polishing process is a process of grind | polishing a grinding | polishing target object using the polishing liquid containing slurry S1. A 2nd grinding | polishing process is a process of further grind | polishing the grinding | polishing target object in which the 1st grinding | polishing process was performed using the polishing liquid containing slurry S2.
なお、例えば不織布にポリウレタンを含浸させた構成の研磨パッドは、上記軟質発泡ポリウレタン製の表面を有する研磨パッドの概念には含まれない。 Examples of the polishing pad that can be preferably used in the second polishing step include a polishing pad having a surface made of soft polyurethane foam, that is, a polishing pad configured to be used by pressing the surface made of soft polyurethane foam against an object to be polished. . Here, the concept of a polishing pad having a surface made of soft foamed polyurethane includes a pad made entirely of soft foamed polyurethane, or a pad base material (also called a base base material) such as a nonwoven fabric or a polyethylene terephthalate (PET) film. .)) And a polishing pad having a structure in which a layer of soft polyurethane foam is provided. In particular, it is preferable to use a so-called suede type polishing pad having a soft foamed polyurethane layer produced by a wet film forming method on a base substrate. By performing the second polishing step using a suede type polishing pad, a higher quality surface (for example, a smaller surface roughness Ra) tends to be obtained.
For example, a polishing pad having a structure in which polyurethane is impregnated with a nonwoven fabric is not included in the concept of the polishing pad having the surface made of the soft foam polyurethane.
この明細書により開示される事項には、上述した研磨方法を実施することを含む研磨物の製造方法(例えば、窒化ガリウム基板または酸化ガリウム素基板の製造方法)および該方法により製造された研磨物の提供が含まれ得る。すなわち、この明細書により、ここに開示されるいずれかの研磨方法を適用して研磨対象物を研磨することを含む、研磨物の製造方法および該方法により製造された研磨物が提供される。上記製造方法によると、高品質な表面を有する研磨物(例えば、窒化ガリウム基板、酸化ガリウム素基板等)が効率的に提供され得る。 <Manufacturing method of polished article>
The matters disclosed by this specification include a method for producing a polished article (for example, a method for producing a gallium nitride substrate or a gallium oxide substrate) including performing the above-described polishing method, and a polished article produced by the method. Offerings may be included. That is, this specification provides a method for producing a polished article and a polished article produced by the method, which include polishing any object to be polished by applying any of the polishing methods disclosed herein. According to the above manufacturing method, a polished product (for example, a gallium nitride substrate, a gallium oxide substrate, etc.) having a high-quality surface can be efficiently provided.
<研磨用組成物の調製>
表1に示す組成を有す研磨用組成物を調製した。シリカ砥粒としては、平均二次粒子径(D50)が65nmの、球状のコロイダルシリカを使用した。表1中、HEDPはヒドロキシエチリデンジホスホン酸、EDTPOはエチレンジアミンテトラ(メチレンホスホン酸)、EAPはエチルアシッドホスフェートを表し、これらは化合物Cphoに該当する。なお、ここで使用したEAPは、リン酸のモノエステルとジエステルとの混合物であり、それらの重量分率に基づく重量平均分子量は140である。また、表1中、TTHAはトリエチレンテトラミン六酢酸、DTPAはジエチレントリアミン五酢酸を表し、これらはリン酸基もホスホン酸基も有しないため、化合物Cphoに該当しない。表1に示す成分の他、実施例1-3の研磨用組成物にはEDTPOを溶解させるために0.6%の水酸化カリウムを含有させ、比較例1-3、1-4の研磨用組成物にはTTHA、DTPAを溶解させるために0.3%の水酸化カリウムを含有させた。各例に係る研磨用組成物の残部は水からなる。表1には、各例に係る研磨用組成物のpHを併せて示している。 <Test Example 1>
<Preparation of polishing composition>
Polishing compositions having the compositions shown in Table 1 were prepared. As the silica abrasive grains, spherical colloidal silica having an average secondary particle diameter (D50) of 65 nm was used. In Table 1, HEDP represents hydroxyethylidene diphosphonic acid, EDTPO represents ethylenediaminetetra (methylenephosphonic acid), and EAP represents ethyl acid phosphate, which correspond to compound Cpho . EAP used here is a mixture of monoester and diester of phosphoric acid, and the weight average molecular weight based on their weight fraction is 140. Moreover, in Table 1, TTHA represents triethylenetetramine hexaacetic acid and DTPA represents diethylenetriaminepentaacetic acid, and these do not correspond to the compound C pho because they have neither a phosphate group nor a phosphonic acid group. In addition to the components shown in Table 1, the polishing composition of Example 1-3 contained 0.6% potassium hydroxide to dissolve EDTPO, and the polishing compositions of Comparative Examples 1-3 and 1-4 were used. The composition contained 0.3% potassium hydroxide to dissolve TTHA and DTPA. The balance of the polishing composition according to each example is made of water. Table 1 also shows the pH of the polishing composition according to each example.
各例に係る研磨用組成物をそのまま研磨液として使用し、市販のノンドープ(n型)自立型GaNウェーハの(0001)面、すなわちC面を、下記のポリシング条件で研磨した。使用したGaNウェーハはいずれも、直径2インチの円形である。
[ポリシング条件]
研磨装置:不二越機械工業社製の片面研磨機装置、型式「RDP-500」
研磨パッド:軟質発泡ポリウレタン製スウェードパッド(フジミインコーポレーテッド社製、Surfin 019-3、AskerC硬度:58)
研磨圧力:45kPa
研磨液供給レート:20mL/分(掛け流し)
平均線速度:1.5m/秒
研磨時間:60分 <Polishing efficiency>
The polishing composition according to each example was directly used as a polishing liquid, and the (0001) plane, that is, the C plane of a commercially available non-doped (n-type) freestanding GaN wafer was polished under the following polishing conditions. All of the used GaN wafers are circular with a diameter of 2 inches.
[Policing condition]
Polishing device: One-side polishing machine manufactured by Fujikoshi Machine Industry Co., Ltd. Model “RDP-500”
Polishing pad: Suede pad made of soft polyurethane foam (Fujimi Incorporated, Surfin 019-3, Asker C hardness: 58)
Polishing pressure: 45kPa
Polishing liquid supply rate: 20 mL / min (flowing)
Average linear velocity: 1.5 m / sec Polishing time: 60 minutes
(1) ΔV=(W0-W1)/ρ
(2) Δx=Δ/S
(3) R=Δx/t
ここで、
W0:研磨前におけるウェーハの重量、
W1:研磨後におけるウェーハの重量、
ρ:GaNの比重(6.15g/cm3)、
ΔV:研磨によるウェーハの体積変化量、
S:ウェーハの表面積、
Δx:研磨によるウェーハの厚さ変化量、
t:研磨時間(60分)、
R:研磨能率、である。 Based on the weight of the wafer before and after the polishing, the polishing efficiency was calculated according to the following calculation formulas (1) to (3). The results are shown in Table 1.
(1) ΔV = (W0−W1) / ρ
(2) Δx = Δ / S
(3) R = Δx / t
here,
W0: Weight of wafer before polishing,
W1: Weight of wafer after polishing,
ρ: Specific gravity of GaN (6.15 g / cm 3 ),
ΔV: Volume change of wafer due to polishing,
S: surface area of the wafer,
Δx: wafer thickness change due to polishing,
t: Polishing time (60 minutes)
R: Polishing efficiency.
各例に係る研磨用組成物を用いて上記ポリシングを行った後のウェーハ表面について、以下の条件で表面粗さRaを測定した。結果を表1に示す。
[Ra測定条件]
評価装置:bruker社製 原子間力顕微鏡(AFM)
装置型式:nanoscope V
視野角:10μm角
走査速度:1Hz(20μm/秒)
走査あたりの測定点数:256(点)
走査本数:256(本)
測定部位:5(ウェーハ中心部の1か所と、該ウェーハの1/2半径部の周上における90°間隔の4か所について測定を行い、上記5か所における測定結果の平均をRaとして記録した。) <Surface roughness Ra>
About the wafer surface after performing the said polishing using the polishing composition which concerns on each example, surface roughness Ra was measured on condition of the following. The results are shown in Table 1.
[Ra measurement conditions]
Evaluation device: atomic force microscope (AFM) manufactured by Bruker
Device model: nanoscope V
Viewing angle: 10 μm square Scanning speed: 1 Hz (20 μm / sec)
Number of measurement points per scan: 256 (points)
Number of scans: 256 (books)
Measurement site: 5 (Measured at one location in the center of the wafer and 4 locations at 90 ° intervals on the circumference of the ½ radius portion of the wafer, and the average of the measurement results at the above 5 locations is defined as Ra. Recorded.)
上記表面粗さRaの測定で得られた5つのAFM像を利用して、各AFM像内に存在するピットの個数を目視でカウントした。このとき、直径100nm以上かつ基準面に対する深さが2nm以上の円形の凹み欠陥をピットとして認定した。その結果に基づいて、以下の0点~4点の5水準でピット抑制性能を評価し、表1に示した。点数が高いほどピット抑制性能が高いといえる。
4点:5つのAFM像の全てにおいてピットの存在は認められない。
3点:5つのAFM像のうち1つでピットが確認される。
2点:5つのAFM像のうち2つでピットが確認されるか、または、
少なくとも1つのAFM像において3個以上のピットが確認される。
1点:5つのAFM像のうち3つ以上でピットが確認されるか、または、
少なくとも1つのAFM像において5個以上のピットが確認される。
0点:表面状態が粗く、ピットの個数をカウントできない。 <Pit suppression performance>
Using the five AFM images obtained by measuring the surface roughness Ra, the number of pits present in each AFM image was visually counted. At this time, a circular dent defect having a diameter of 100 nm or more and a depth of 2 nm or more with respect to the reference surface was recognized as a pit. Based on the results, the pit suppression performance was evaluated at the following five levels of 0 to 4 points and shown in Table 1. The higher the score, the higher the pit suppression performance.
4 points: No pits are observed in all 5 AFM images.
3 points: A pit is confirmed in one of the five AFM images.
2 points: pits are confirmed in 2 out of 5 AFM images, or
Three or more pits are confirmed in at least one AFM image.
1 point: Pit is confirmed in 3 or more of 5 AFM images, or
Five or more pits are confirmed in at least one AFM image.
0 point: The surface state is rough and the number of pits cannot be counted.
すなわち、酸化剤を含有しない実施例1-6の研磨用組成物に、表2に示す濃度で酸化剤としての過硫酸ナトリウムまたはH2O2をさらに含有させることにより、比較例1-5、1-6に係る研磨用組成物を調製した。また、酸化剤を含有しない実施例1-11の研磨用組成物に、表2に示す濃度で酸化剤としてのH2O2をさらに含有させることにより、比較例1-7に係る研磨用組成物を調製した。これらの比較例に係る研磨用組成物について、上記と同様にしてGaNウェーハの研磨を行い、ピット抑制性能を評価した。結果を表2に示す。 In order to investigate the influence of the inclusion of the oxidizing agent, the following experiment was further conducted.
That is, Comparative Example 1-5 by adding sodium persulfate or H 2 O 2 as an oxidizing agent to the polishing composition of Example 1-6 that does not contain an oxidizing agent at the concentrations shown in Table 2. A polishing composition according to 1-6 was prepared. Further, the polishing composition according to Comparative Example 1-7 was further added with H 2 O 2 as an oxidizing agent at a concentration shown in Table 2 in the polishing composition of Example 1-11 containing no oxidizing agent. A product was prepared. About the polishing composition which concerns on these comparative examples, the GaN wafer was grind | polished similarly to the above, and pit suppression performance was evaluated. The results are shown in Table 2.
<研磨用組成物の調製>
砥粒および添加剤を表3、4の各例に示す濃度で含むスラリーS1、S2を調製した。表3、4の砥粒種の欄において、「S」はシリカ砥粒を表し、「A」はアルミナ砥粒を表す。上記シリカ砥粒としては、平均二次粒子径(D50)が65nmの、球状のコロイダルシリカを使用した。上記アルミナ砥粒としては、平均二次粒子径(D50)が450nmのα-アルミナを使用した。また、表3中、スラリーS2の添加剤の欄において、HEDPはヒドロキシエチリデンジホスホン酸、EDTPOはエチレンジアミンテトラ(メチレンホスホン酸)を表し、これらはいずれも化合物Cphoに該当する。実施例2-10のスラリーS2には、表3に示す成分の他、EDTPOを溶解させるために0.6%の水酸化カリウムを含有させた。各例に係るスラリーS1、S2の残部は水からなる。表3、4には、各例に係るスラリーS1、S2のpHを併せて示している。 <Test Example 2>
<Preparation of polishing composition>
Slurries S1 and S2 containing abrasive grains and additives at concentrations shown in Tables 3 and 4 were prepared. In the column of abrasive grain types in Tables 3 and 4, “S” represents silica abrasive grains, and “A” represents alumina abrasive grains. As the silica abrasive, spherical colloidal silica having an average secondary particle diameter (D50) of 65 nm was used. As the alumina abrasive grains, α-alumina having an average secondary particle diameter (D50) of 450 nm was used. Moreover, in Table 3, in the column of the additive of the slurry S2, HEDP represents hydroxyethylidene diphosphonic acid, and EDTPO represents ethylenediaminetetra (methylenephosphonic acid), both of which correspond to the compound Cpho . In addition to the components shown in Table 3, the slurry S2 of Example 2-10 contained 0.6% potassium hydroxide in order to dissolve EDTPO. The remainder of the slurries S1 and S2 according to each example is made of water. Tables 3 and 4 also show the pH of the slurries S1 and S2 according to each example.
(第一研磨工程)
上記で調製したスラリーS1をそのまま研磨液として使用して、市販のノンドープ(n型)自立型GaNウェーハの(0001)面、すなわちC面を、下記のポリシング条件で研磨した。使用したGaNウェーハはいずれも、直径2インチの円形である。
[ポリシング条件]
研磨装置:日本エンギス社製の片面研磨装置、型式「EJ-380IN」
研磨パッド:表3に示すとおり。
研磨圧力:30kPa
研磨液供給レート:20mL/分(掛け流し)
平均線速度:1.0m/秒
研磨時間:表3に示すとおり。 <Polishing GaN substrate>
(First polishing process)
Using the slurry S1 prepared above as a polishing liquid, the (0001) plane, that is, the C plane of a commercially available non-doped (n-type) freestanding GaN wafer was polished under the following polishing conditions. All of the used GaN wafers are circular with a diameter of 2 inches.
[Policing condition]
Polishing device: Single-side polishing device manufactured by Nippon Engis Co., Ltd. Model “EJ-380IN”
Polishing pad: As shown in Table 3.
Polishing pressure: 30kPa
Polishing liquid supply rate: 20 mL / min (flowing)
Average linear velocity: 1.0 m / sec Polishing time: As shown in Table 3.
次いで、上記で調製したスラリーS2をそのまま研磨液として使用して、第一研磨工程を実施した後のGaNウェーハの表面に対して第二研磨工程を実施した。第二研磨工程は、研磨パッドおよび研磨時間を表4に示すとおりとした他は、第一研磨工程と同様のポリシング条件により行った。ただし、比較例2-1~2-4では第二研磨工程は行わなかった。 (Second polishing step)
Next, using the slurry S2 prepared above as a polishing liquid, the second polishing step was performed on the surface of the GaN wafer after the first polishing step was performed. The second polishing step was performed under the same polishing conditions as the first polishing step except that the polishing pad and the polishing time were as shown in Table 4. However, in Comparative Examples 2-1 to 2-4, the second polishing step was not performed.
研磨後のウェーハ表面について、以下の条件で表面粗さRaを測定した。結果を表3、4に示す。
[Ra測定条件]
評価装置:bruker社製 原子間力顕微鏡(AFM)
装置型式:nanoscope V
視野角:10μm角
走査あたりの測定点数:256(点)
走査本数:256(本)
測定部位:5(ウェーハ中心部の1か所と、該ウェーハの1/2半径部の周上における90°間隔の4か所について測定を行い、上記5か所における測定結果の平均をRaとして記録した。) <Surface roughness Ra>
The surface roughness Ra of the polished wafer surface was measured under the following conditions. The results are shown in Tables 3 and 4.
[Ra measurement conditions]
Evaluation device: atomic force microscope (AFM) manufactured by Bruker
Device model: nanoscope V
Viewing angle: 10 μm square Number of measurement points per scan: 256 (points)
Number of scans: 256 (books)
Measurement site: 5 (Measured at one location in the center of the wafer and 4 locations at 90 ° intervals on the circumference of the ½ radius portion of the wafer, and the average of the measurement results at the above 5 locations is defined as Ra. Recorded.)
Claims (20)
- ガリウム化合物系半導体基板の研磨に用いられる研磨用組成物であって、
シリカ砥粒;
リン酸基またはホスホン酸基を有する化合物Cpho;および、
水;
を含み、かつ酸化剤を含有しない、研磨用組成物。 A polishing composition used for polishing a gallium compound semiconductor substrate,
Silica abrasive grains;
A compound C pho having a phosphoric acid group or a phosphonic acid group; and
water;
And a polishing composition containing no oxidizing agent. - 前記化合物Cphoとして、ホスホン酸基を有するキレート化合物を含む、請求項1に記載の研磨用組成物。 The polishing composition according to claim 1, comprising a chelate compound having a phosphonic acid group as the compound Cpho .
- 前記化合物Cphoとして、リン酸モノC1-4アルキルエステル、リン酸ジC1-4アルキルエステルおよび亜リン酸モノC1-4アルキルエステルからなる群から選択される少なくとも一種の化合物を含む、請求項1または2に記載の研磨用組成物。 As the compound C pho, comprising at least one compound selected phosphoric acid mono C 1-4 alkyl ester, from phosphoric acid di C 1-4 alkyl ester and the group consisting of phosphorous acid mono C 1-4 alkyl ester, The polishing composition according to claim 1 or 2.
- 前記化合物Cphoとして、リン酸および亜リン酸の少なくとも一方を含む、請求項1または2に記載の研磨用組成物。 The polishing composition according to claim 1 or 2, comprising at least one of phosphoric acid and phosphorous acid as the compound Cpho .
- 前記化合物Cphoとして、リン酸の無機塩および亜リン酸の無機塩からなる群から選択される少なくとも一種の化合物を含む、請求項1または2に記載の研磨用組成物。 The polishing composition according to claim 1 or 2, comprising at least one compound selected from the group consisting of an inorganic salt of phosphoric acid and an inorganic salt of phosphorous acid as the compound Cpho .
- pHが2未満である、請求項1から5のいずれか一項に記載の研磨用組成物。 The polishing composition according to any one of claims 1 to 5, wherein the pH is less than 2.
- さらに酸を含む、請求項1から6のいずれか一項に記載の研磨用組成物。 The polishing composition according to any one of claims 1 to 6, further comprising an acid.
- 前記化合物Cphoの含有量m1[モル/kg]と前記酸の含有量m2[モル/kg]との関係が、以下の式:
m1/(m1+m2)≧0.1;
を満たす、請求項7に記載の研磨用組成物。 The relation between the content m1 [mol / kg] of the compound Cpho and the content m2 [mol / kg] of the acid is represented by the following formula:
m1 / (m1 + m2) ≧ 0.1;
The polishing composition according to claim 7, wherein - 前記ガリウム化合物系半導体基板は、窒化ガリウム基板または酸化ガリウム基板である、請求項1から8のいずれか一項に記載の研磨用組成物。 The polishing composition according to any one of claims 1 to 8, wherein the gallium compound semiconductor substrate is a gallium nitride substrate or a gallium oxide substrate.
- 請求項1から9のいずれか一項に記載の研磨用組成物をガリウム化合物系半導体基板に供給して該基板を研磨することを含む、研磨方法。 A polishing method comprising supplying the polishing composition according to any one of claims 1 to 9 to a gallium compound semiconductor substrate and polishing the substrate.
- ガリウム化合物系半導体基板を研磨する方法であって、
砥粒A1および水を含むスラリーS1で研磨する第一研磨工程と、
砥粒A2および水を含むスラリーS2で研磨する第二研磨工程と、
をこの順で含み、
ここで、前記砥粒A2はシリカ砥粒を含み、
前記スラリーS2は、リン酸基またはホスホン酸基を有する化合物Cphoをさらに含み、
前記スラリーS1は、前記化合物Cphoを含まないか、または前記化合物Cphoの濃度[重量%]が前記スラリーS2における前記化合物Cphoの濃度[重量%]より低い、研磨方法。 A method for polishing a gallium compound semiconductor substrate,
A first polishing step of polishing with a slurry S1 containing abrasive grains A1 and water;
A second polishing step of polishing with a slurry S2 containing abrasive grains A2 and water;
In this order,
Here, the abrasive grains A2 include silica abrasive grains,
The slurry S2 further includes a compound Cpho having a phosphoric acid group or a phosphonic acid group,
The slurry S1 is does not contain the compound C pho, or the concentration of the compound C pho [wt%] is lower than the concentration [wt%] of the compound C pho in the slurry S2, the polishing method. - 前記スラリーS1のpHが2.0未満である、請求項11に記載の研磨方法。 The polishing method according to claim 11, wherein the pH of the slurry S1 is less than 2.0.
- 前記スラリーS1は強酸を含む、請求項11または12に記載の研磨方法。 The polishing method according to claim 11 or 12, wherein the slurry S1 contains a strong acid.
- 前記スラリーS1は酸化剤を含む、請求項11から13のいずれか一項に記載の研磨方法。 The polishing method according to any one of claims 11 to 13, wherein the slurry S1 contains an oxidizing agent.
- 前記酸化剤は、過マンガン酸塩、メタバナジン酸塩および過硫酸塩からなる群から選択される少なくとも一つを含む、請求項14に記載の研磨方法。 The polishing method according to claim 14, wherein the oxidizing agent includes at least one selected from the group consisting of permanganate, metavanadate and persulfate.
- 前記砥粒A1はシリカ砥粒を含む、請求項11から15のいずれか一項に記載の研磨方法。 The polishing method according to any one of claims 11 to 15, wherein the abrasive grains A1 include silica abrasive grains.
- 前記スラリーS2のpHが3.0未満である、請求項11から16のいずれか一項に記載の研磨方法。 The polishing method according to any one of claims 11 to 16, wherein the pH of the slurry S2 is less than 3.0.
- 前記スラリーS2における前記化合物Cphoの濃度が0.2重量%以上15重量%以下である、請求項11から17のいずれか一項に記載の研磨方法。 The polishing method according to any one of claims 11 to 17, wherein a concentration of the compound Cpho in the slurry S2 is 0.2 wt% or more and 15 wt% or less.
- 前記第二研磨工程では、軟質発泡ポリウレタン製の表面を有する研磨パッドを用いて研磨する、請求項11から18のいずれか一項に記載の研磨方法。 The polishing method according to any one of claims 11 to 18, wherein in the second polishing step, polishing is performed using a polishing pad having a surface made of soft foamed polyurethane.
- 請求項11から19のいずれか一項に記載の研磨方法に用いられる研磨用組成物セットであって、
前記スラリーS1またはその濃縮液である組成物Q1と、
前記スラリーS2またはその濃縮液である組成物Q2と
を含み、
前記組成物Q1と前記組成物Q2とは互いに分けて保管されている、研磨用組成物セット。 A polishing composition set used in the polishing method according to any one of claims 11 to 19,
A composition Q1 which is the slurry S1 or a concentrated solution thereof;
Including the slurry S2 or a composition Q2 which is a concentrated liquid thereof,
The polishing composition set in which the composition Q1 and the composition Q2 are stored separately from each other.
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JP2020509937A JP7424967B2 (en) | 2018-03-28 | 2019-03-22 | Gallium compound-based semiconductor substrate polishing composition |
US17/040,355 US20210024781A1 (en) | 2018-03-28 | 2019-03-22 | Gallium compound-based semiconductor substrate polishing composition |
KR1020207030592A KR20200135851A (en) | 2018-03-28 | 2019-03-22 | Gallium compound based semiconductor substrate polishing composition |
US17/975,805 US20230063355A1 (en) | 2018-03-28 | 2022-10-28 | Gallium compound-based semiconductor substrate polishing composition |
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TW201942321A (en) | 2019-11-01 |
US20230063355A1 (en) | 2023-03-02 |
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JPWO2019188747A1 (en) | 2021-04-08 |
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EP3780069A4 (en) | 2022-04-06 |
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